Iridoides DINDA

Chem. Pharm. Bull.
57(8) 765796 (2009)
August 2009
765
Review
Naturally Occurring Iridoids, Secoiridoids and Their
Bioactivity. An Updated Review, Part 3
Biswanath DINDA,* Debashis ROY CHOWDHURY, and Bikas Chandra MOHANTA
Department of Chemistry, Tripura University; Suryamaninagar, Agartala 799130, India.
Received April 5, 2009; accepted May 13, 2009; published online June 1, 2009
Naturally occurring new iridoids and secoiridoids published during 20052008 are reviewed with available
physical and spectral data: mp, [a ]D, UV, IR, 1H- and 13C-NMR and plant source. The works on biological and
pharmacological activity of naturally occurring iridoids and secoiridoids reported during 20052008 are also
reviewed. Bioactivities like antibacterial, anticancer, anticoagulant, antifungal, anti-inflammatory, antioxidative,
antiprotozoal, hepatoprotective and neuroprotective activities are highlighted.
Key words
iridoid; secoiridoid; physical data; spectral data; plant source; bioactivity
This is the third part of a review1,2) and is mainly a compilation of new iridoids and secoiridoids reported in the literature during mid 20052008 as well as a highlight of biological and pharmacological activity of iridoids and secoiridoids
published in the said period. The earlier parts of the review1,2) discussed the new naturally occurring iridoids and
secoiridoids reported during 1994mid 2005 as well as biological and pharmacological activities published in the said
period.
Iridoids and secoiridoids are useful phytochemicals in a
number of folk medicinal plants and many of them possess
significant biological and pharmacological activities. Some
of them are chemotaxonomically useful as markers of genus
in various plant families. The main aim of this review is for
rapid identification of isolated iridoids and secoiridoids by
comparison of spectral data as well as to highlight the importance of this class of phytochemicals as pharmaceutical raw
materials in the design of several synthetic potent drugs and
formulations of herbal drugs.
A number of review articles on plant iridoids and secoiridoids are available. Earlier compilation of plant iridoids and
secoiridoids reported upto 1993 is provided in four review
articles.36)
Iridoids and secoiridoids are listed in Table 1 in a fashion
similar to that of earlier reviews.1,2) All the compounds are
arranged in six groups. Group 1 contains iridoid glycosides
with an eight carbon skeleton; Group 2 contains iridoid glycosides with a nine-carbon skeleton and is further divided in
to subgroups depending on whether the ninth carbon is attached to C-4 (Group 2a) or C-8 (Group 2b); Group 3 contains iridoid glycosides with ten-carbon skeletons and divided into subgroups; Group 4 contains secoiridoid glycosides; Group 5 contains iridoid aglycones and derivatives and
Group 6 contains bis- and tetrakis-iridoid glycosides. The
available data for each compound were listed in the following
order: name; structure; molecular formula; calculated molecular weight as per atomic weight of most abundant isotopic
To whom correspondence should be addressed.
atoms of C, H, O, N, S, etc.; melting point (C) of crystalline

compound; optical rotation, [a ]D (with concentration and
solvent); UV (solvent, l max in nm, log e ); IR (medium, n max
in cm1); 1H-NMR (spectrometer frequency, solvent); chemical shifts (in d , ppm starting with H-1 and listed in order)
with multiplicities, coupling constants in Hz, assignments;
13
C-NMR (spectrometer frequency, solvent); chemical shifts
(in d , ppm, starting with C-1 and listed in order) with assignments; plant source (family); reference(s). The 1H-NMR data
have been rounded to the second decimal point and the 13CNMR data to the first decimal point. Assignment with the
same superscript may be interchanged. Data for the derivatives were not listed unless the derivative rather than the free
compound isolated in free state.
Numbering of the iridoid or secoiridoid skeleton and of
the most common functionalities is given in Fig. 1. The sugar
or substituent on the C-1 carbon of the aglycone moiety is
given the single prime () designation, while other substituents are designated as double prime (), triple prime (),
etc., according to their substitution position on the main iridoid or secoiridoid skeleton, except in cases of substituents
on other substituents. The designation of substituents on
other substituents is done by succeeded primes; for instance ,
a p-coumaroyl unit on sugar unit at C-1 will be designated as
double prime and a sugar unit on p-coumaroyl unit will be
designated as triple prime (e.g., 1d). For bis- and tetrakis-iridoids, the monomeric units are designated as units a,b,c, and
d and these units are numbered as per usual numbering. Cinnamoyl, coumaroyl, caffeoyl, feruloyl, isoferuloyl groups are
in trans configuration unless otherwise indicated. Some
abbreviations used in representation of structures are: Glc: b D-glucopyranosyl; Rha: a -L-rhamnopyranosyl; Me: methyl;
OMe: methoxy. Suspected errors in a numbering of a
monomeric unit and in multiplicity of proton coupling were
corrected if there was some ambiguity in the numbering or
multiplicity of proton coupling for a particular compound
was observed. All the compounds in Table 1 are alphabeti-
e-mail: [email protected]
2009 Pharmaceutical Society of Japan
766
Vol. 57, No. 8
Table 1.
List of New Iridoids

Group 1 (8-Carbon skeleton)
1.
Globularioside
C24H29ClO11: 528.1398; amorphous solid; [a ]D20 25.0 (c0.01, MeOH); 1H-NMR (300 MHz, CD3OD): 5.63 (d,
3.6, H-1), 6.22 (dd, 6.0, 1.5, H-3), 5.06 (dd, 6.0, 3.4, H-4), 2.70 (m, H-5), 3.94 (dd, 7.2, 3.6, H-6), 4.08 (d, 7.2, H-7),
2.63 (dd, 9.9, 3.6, H-9), 4.32 (d, 12.0, H-10), 5.06 (d, 12.0, H-10), 4.75 (d, 7.8, H-1), 3.18 (m, H-2), 3.30 (m, H-3),
3.69 (m, H-4, 5), 3.65 (dd, 11.8, 5.8, H-6), 3.89 (dd, 11.8, 2.0, H-6), 7.62 (br s, H-2, 6), 7.41 (br s, H-3,5), 7.40
(br s, H-4), 7.73 (d, 16.2, H-7), 6.53 (d, 16.2, H-8); 13C-NMR (75 MHz, CD3OD): 96.5 (C-1), 141.7 (C-3), 106.7
(C-4), 39.9 (C-5), 80.5 (C-6), 67.2 (C-7), 84.5 (C-8), 44.6 (C-9), 66.6 (C-10), 101.3 (C-1), 75.7 (C-2), 79.6 (C-3),
72.3 (C-4), 80.0 (C-5), 63.6 (C-6), 136.6 (C-1), 130.9 (C-2, 6), 130.1 (C-3, 5), 132.4 (C-4), 119.6 (C-7),
147.5 (C-8). Globularia alypum (Globulariaceae).7)
Group 2a (9-Carbon skeleton; ninth carbon on C-4)
2.
Citrifoside
C16H22O10: 374.1213; colorless amorphous solid; [a ]D20 56.8 (c0.105, MeOH); UV (MeOH): 235.4 (3.86); IR (KBr): 3350,
1700, 1635, 1439, 1369, 1286, 1180, 1156, 1072, 1022, 1004; 1H-NMR (500 MHz, DMSO-d6): 5.28 (d, 4.0, H-1), 7.37 (s, H3), 3.53 (d, 8.1, H-5), 5.97 (d, 5.2, H-6), 5.72 (d, 5.2, H-7), 4.57 (m, H-8), 2.22 (m, H-9), 3.64 (s, OMe), 4.48 (d, 7.9, H-1),
2.99 (dd, 8.0, 7.9, H-2), 3.16 (m, H-3), 3.07 (m, H-4), 3.13 (m, H-5), 3.67 (m, H-6), 3.45 (dd, 11.8, 5.9, H-6); 13C-NMR
(125 MHz, DMSO-d6): 95.2 (C-1), 150.8 (C-3), 109.9 (C-4), 37.1 (C-5), 134.0 (C-6), 134.3 (C-7), 76.3 (C-8), 49.5 (C-9), 166.6
(C-11), 51.0 (OMe), 98.7 (C-1), 73.0 (C-2), 76.7 (C-3), 69.9 (C-4), 77.2 (C-5), 60.9 (C-6). Morinda citrifolia
(Rubiaceae).8)
3.
Group 2b (9-Carbon skeleton; ninth carbon on C-8)

7,8-Dehydroharpagide
C15H22O9: 346.1263; amorphous powder; [a ]D25 108.0 (c0.5, MeOH); UV (MeOH): 223 (2.9); IR (KBr): 35003100, 2928,
2850, 1640, 1470, 10301010, 980; 1H-NMR (500 MHz, CDCl3drop DMSO-d6): 5.34 (d, 1.8, H-1), 5.50 (d, 6.7, H-3), 4.90
(dd, 6.7, 2.4, H-4), 4.30 (d, 5.1, H-6), 5.70 (d, 6.3, H-7), 3.00 (d, 3.1, H-9), 1.40 (s, H3-10), 4.65 (d, 7.6, H-1), 3.60 (m, H-2),
3.30 (m, H-3), 3.40 (m, H-4), 3.49 (m, H-5), 3.68 (m, H-6), 3.58 (m, H-6); 13C-NMR (125 MHz, CDCl3drop DMSO-d6):
96.0 (C-1), 144.2 (C-3), 108.6 (C-4), 74.6 (C-5), 78.4 (C-6), 119.5 (C-7), 134.6 (C-8), 56.9 (C-9), 21.8 (C-10), 101.3 (C-1), 73.7
(C-2), 76.4 (C-3), 70.0 (C-4), 77.1 (C-5), 61.5 (C-6). Ajuga remota (Labiatae).9)
4.
6-O-Acetylantirrinoside
C17H24O11: 404.1318; gum; [a ]D 100.0 (c0.04, MeOH); UV (MeOH): 275 (2.24), 202 (3.61); IR (film): 3411, 2923, 1734,
1375, 1240, 1101, 1076, 1047, 1016, 960; 1H-NMR (500 MHz, CD3OD): 5.44 (d, 6.0, H-1), 6.32 (d, 6.5, H-3), 4.82 (d, 6.5, H-4),
4.86 (d, 2.0, H-6), 3.39 (d, 2.0, H-7), 2.36 (d, 6.0, H-9), 1.39 (s, H3-10), 4.57 (d, 8.0, H-1), 3.14 (m, H-2), 3.30 (m, H-3, 5),
3.15 (m, H-4), 3.53 (dd, 11.8, 6.5, H-6), 3.83 (dd, 11.8, 2.5, H-6), 2.03 (s, Ac); 13C-NMR (125 MHz, CD3OD): 94.6 (C-1),
143.4 (C-3), 107.5 (C-4), 74.7 (C-5), 79.4 (C-6), 64.2 (C-7), 64.5 (C-8), 53.3 (C-9), 17.4 (C-10), 99.8 (C-1), 74.7 (C-2), 77.7
(C-3), 71.8 (C-4), 78.6 (C-5), 63.0 (C-6), 20.3, 172.0 (Ac). Kickxia abhaica (Scrophulariaceae).10)
5.
6-O-p-Hydroxybenzoylantirrinoside
C22H26O12: 482.1424; amorphous powder; [a ]D 51.3 (c0.07, MeOH); UV (MeOH): 320 (3.62), 257 (4.58),
202 (4.82); IR (film): 3420, 3411, 2920, 1701, 1608, 1313, 1279, 1236, 1167, 1101, 1074, 1045, 1012, 771, 617;
1
H-NMR (500 MHz, CD3OD): 4.99 (d, 8.0, H-1), 6.24 (d, 6.0, H-3), 4.77 (d, 6.0, H-4), 3.69 (d, 1.0, H-6), 3.15
(br s, H-7), 2.22 (d, 8.0, H-9), 1.24 (s, H3-10), 4.62 (d, 8.0, H-1), 3.16 (m, H-2), 3.49 (m, H-3), 3.32 (m, H-4),
3.33 (m, H-5), 4.40 (dd, 12.0, 7.0, H-6), 4.52 (dd, 12.0, 2.5, H-6), 7.78 (d, 9.0, H-2, 6), 6.73 (d, 9.0, H-3, 5);
13
C-NMR (125 MHz, CD3OD): 95.6 (C-1), 142.8 (C-3), 107.7 (C-4), 74.8 (C-5), 78.8 (C-6), 66.0 (C-7), 63.0 (C8), 53.3 (C-9), 17.6 (C-10), 99.9 (C-1), 74.8 (C-2), 75.7 (C-3), 71.8 (C-4), 77.7 (C-5), 64.1 (C-6), 122.2 (C1), 132.9 (C-2, 6), 132.9 (C-3, 5), 163.7 (C-4), 167.8 (C-7). Kickxia abhaica (Scrophulariaceae).10)
Harprocumbide B (6-O-(cis-p-Coumaroyl procumbide))
C24H28O12: 508.1580; white amorphous powder; 1H-NMR (400 MHz, C5D5N): 6.05 (d, 9.2, H-1), 6.67 (d, 6.2, H3), 5.23 (d, 6.2, H-4), 4.35 (s, H-6), 3.66 (s, H-7), 2.62 (d, 9.2, H-9), 1.81 (s, H3-10), 5.37 (d, 8.0, H-1), 4.07 (t,
8.4, H-2), 4.22 (t, 8.8, H-3), 4.14 (m, H-4), 3.97 (dd, 5.2, 2.4, H-5), 4.89 (dd, 12.0, 2.3, H-6), 4.83 (dd, 12.0,
5.2, H-6), 8.02 (d, 8.4, H-2, 6), 7.12 (d, 8.4, H-3, 5), 6.79 (d, 12.8, H-7), 5.92 (d, 12.8, H-8); 13C-NMR
(100 MHz, C5D5N): 96.0 (C-1), 142.7 (C-3), 105.1 (C-4), 79.6 (C-5), 77.4 (C-6), 65.4 (C-7), 66.2 (C-8), 52.6 (C9), 17.6 (C-10), 100.1 (C-1), 74.7 (C-2), 78.0 (C-3), 71.0 (C-4), 75.2 (C-5), 63.7 (C-6), 126.3 (C-1), 133.6
(C-2, 6), 115.7 (C-3, 5), 160.4 (C-4), 144.5 (C-7), 115.8 (C-8), 166.8 (C-9). Harpagophytum procumbens
(Pedaliaceae).11)
Harpagide 6-O-b -glucoside
C21H34O15: 526.1897; amorphous powder; [a ]D25 57.0 (c1.0,MeOH); UV (MeOH): 226 (2.4); IR (KBr): 35503100, 2920,
2850, 1650, 1475, 10201000, 950; 1H-NMR (500 MHz, DMSO-d6): 5.36 (d, 1.1, H-1), 6.20 (d, 6.7, H-3), 5.94 (dd, 6.7, 1.2, H4), 5.00 (d, 5.6, H-6), 2.18 (m, H-7), 2.08 (m, H-7), 3.14 (d, 1.6, H-9), 1.23 (s, H3-10), 4.60 (d, 7.2, H-1), 3.50 (m, H-2), 3.39 (m,
H-3), 3.20 (m, H-4), 3.29 (m, H-5), 3.56 (m, H-6), 3.47 (m, H-6), 4.84 (d, 7.8, H-1), 3.54 (m, H-2), 3.44 (m, H-3), 3.14 (m,
H-4), 3.36 (m, H-5), 3.68 (m, H-6), 3.48 (m, H-6); 13C-NMR (150 MHz, DMSO-d6): 95.7 (C-1), 146.0 (C-3), 107.8 (C-4),
75.1 (C-5), 76.6 (C-6), 48.3 (C-7), 73.4 (C-8), 55.5 (C-9), 21.4 (C-10), 100.4 (C-1), 74.0 (C-2), 76.1 (C-3), 69.9 (C-4), 76.8
(C-5), 61.6 (C-6), 101.0 (C-1), 73.6 (C-2), 76.5 (C-3), 70.4 (C-4), 77.0 (C-5), 60.9 (C-6 ). Ajuga remota (Labiatae).9)
8-O-Acetylharpagide-6-O-b -glucoside
C23H36O16: 568.2003; amorphous powder; [a ]D25 85.0 (c0.5, MeOH); UV (MeOH): 218 (2.8); IR (KBr): 3540, 2930, 2850,
1740, 1645, 1470, 10401010, 980; 1H-NMR (500 MHz, DMSO-d6): 6.35 (d, 1.5, H-1), 6.45 (d, 6.4, H-3), 6.04 (dd, 6.4, 2.0, H4), 4.90 (d, 4.5, H-6), 2.20 (m, H-7), 2.10 (m, H-7), 3.21 (d, 2.2, H-9) , 1.47 (s, H3-10), 2.04 (s, OAc), 4.80 (d, 7.6, H-1), 3.46 (m,
H-2), 3.38 (m, H-3), 3.25 (m, H-4), 3.30 (m, H-5), 3.55 (m, H-6), 3.41 (m, H-6), 5.01 (d, 7.5, H-1), 3.53 (m, H-2), 3.40 (m,
H-3), 3.18 (m, H-4), 3.28 (m, H-5), 3.58 (m, H-6), 3.44 (m, H-6); 13C-NMR (125 MHz, DMSO-d6): 94.8 (C-1), 145.3 (C-3),
108.4 (C-4), 76.0 (C-5), 75.9 (C-6), 48.6 (C-7), 91.2 (C-8), 56.4 (C-9), 23.4 (C-10), 101.0 (C-1), 74.7 (C-2), 76.8 (C-3), 69.8
(C-4), 76.5 (C-5), 61.0 (C-6), 99.9 (C-1), 74.0 (C-2), 76.7 (C-3), 69.4 (C-4), 60.2 (C-6), 23.8, 170.3 (OAc). Ajuga remota
(Labiatae).9)
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August 2009
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6,7-Dehydro-8-acetylharpagide
C17H24O10: 388.1369; colorless plates; mp 250 C; [a ]D25 19.0 (c0.5, MeOH); UV (MeOH): 214 (3.0); IR (KBr): 3450
3100, 2920, 2850, 1735, 1644, 1470, 1050, 890; 1H-NMR (500 MHz, CDCl3drop DMSO-d6): 5.40 (d, 2.0, H-1), 5.70 (d, 6.2,
H-3), 5.21 (dd, 6.4, 2.2, H-4), 6.02 (d, 9.0, H-6), 5.84 (d, 9.0, H-7), 3.21 (d, 1.8, H-9), 1.37 (s, H3-10), 2.02 (s, OAc), 4.50 (d, 7.4,
H-1), 3.48 (m, H-2), 3.55 (m, H-3), 3.20 (m, H-4), 3.33 (m, H-5), 3.70 (m, H-6), 3.62 (m, H-6); 13C-NMR (125 MHz,
CDCl3drop DMSO-d6): 94.8 (C-1), 143.8 (C-3), 107.3 (C-4), 76.0 (C-5), 133.6 (C-6), 128.7 (C-7), 90.5 (C-8), 47.0 (C-9), 23.0
(C-10), 99.0 (C-1), 74.4 (C-2), 76.9 (C-3), 70.4 (C-4), 77.6 (C-5), 62.1 (C-6), 25.4, 169.8 (OAc). Ajuga remota (Labiatae).9)
6-Keto-8-acetylharpagide
C17H24O11: 404.1318; colorless platelets, mp 250 C; [a ]D25 46.0 (c1.0, MeOH); UV (MeOH): 208 (3.2); IR (KBr): 3540,
3350, 1740, 1700, 1650, 1470, 1350, 10301010, 920, 870; 1H-NMR (500 MHz, CDCl3drop DMSO-d6): 5.40 (d, 1.8, H-1),
5.50 (d, 6.1, H-3), 5.10 (dd, 6.1, 2.0, H-4), 2.40 (d, 6.3, H-7), 2.25 (d, 6.3, H-7), 2.90 (d, 1.6, H-9), 1.50 (s, H3-10), 1.90 (s, OAc),
4.70 (d, 7.5, H-1), 3.43 (m, H-2), 3.29 (m,H-3), 3.36 (m, H-4), 3.52 (m, H-5), 3.80 (m, H-6), 3.68 (m, H-6); 13C-NMR
(125 MHz, CDCl3drop DMSO-d6): 95.4 (C-1), 145.0 (C-3), 109.0 (C-4), 73.7 (C-5), 213.1 (C-6), 49.8 (C-7), 87.3 (C-8), 55.9
(C-9), 22.9 (C-10), 99.4 (C-1), 73.5 (C-2), 77.3 (C-3), 71.4 (C-4), 76.9 (C-5), 61.5 (C-6), 24.6, 171.2 (OAc). Ajuga remota
(Labiatae).9)
6-O-Caffeoylharpagide
C24H30O13: 526.1686; pale brown amorphous powder; [a ]D26 37.6 (c1.0, MeOH); UV (MeOH): 312 (2.60), 227
(2.48), 203 (2.56); IR (KBr): 3394, 1697, 1607, 1605, 1520, 1033;1H-NMR (400 MHz, CD3OD): 5.65 (d, 1.2, H-1),
6.32 (d, 6.4, H-3), 4.93 (dd, 6.4, 1.4, H-4), 3.67 (t, 3.9, H-6), 1.85 (dd, 13.7, 4.6, H-7), 1.75 (dd, 13.8, 3.0, H-7), 2.54
(s, H-9), 1.18 (s, H3-10), 4.59 (d, 7.9, H-1), 3.25 (t, 8.9, H-2), 3.39 (t, 7.4, H-3), 3.40 (t, 7.4, H-4), 3.543.57 (m,
H-5), 4.48 (dd, 12.0, 2.1, H-6), 4.35 (dd, 12.0, 5.8, H-6), 7.03 (d, 2.0, H-2), 6.76 (d, 8.2, H-5), 6.93 (dd, 8.2, 2.0,
H-6), 7.56 (d, 15.9, H-7), 6.28 (d, 15.9, H-8); 13C-NMR (100 MHz, CD3OD): 93.1 (C-1), 142.5 (C-3), 108.4 (C-4),
72.8 (C-5), 78.3 (C-6), 46.9 (C-7), 78.4 (C-8), 59.5 (C-9), 25.0 (C-10), 99.2 (C-1), 74.4 (C-2), 77.4 (C-3), 71.7 (C4), 76.7 (C-5), 64.5 (C-6), 127.7 (C-1), 115.2 (C-2), 146.8 (C-3), 149.6 (C-4), 116.5 (C-5), 123.1 (C-6), 147.2
(C-7), 114.8 (C-8), 169.1 (C-9). Scrophularia ningpoensis (Scrophulariaceae).12)
12. 6-O-Feruloylharpagide
C25H32O13: 540.1842; brown amorphous powder; [a ]D26 35.2 (c1.0, MeOH); UV (MeOH): 325 (2.61), 235 (2.48),
204 (2.58); IR (KBr): 3417, 1601, 1516; 1H-NMR (400 MHz, CD3OD): 5.65 (d, 1.2, H-1), 6.30 (d, 6.4, H-3), 4.93 (dd,
6.4, 1.5, H-4), 3.67 (t, 3.9, H-6), 1.84 (dd, 13.7, 4.6, H-7), 1.73 (dd, 13.7, 3.2, H-7), 2.54 (s, H-9), 1.17 (s, H3-10), 4.59
(d, 7.9, H-1), 3.24 (t, 9.0, H-2), 3.41 (t, 6.2, H-3), 3.40 (t, 6.2, H-4), 3.543.58 (m, H-5), 4.48 (dd, 12.0, 2.2, H6), 4.36 ( dd, 12.0, 5.8, H-6), 7.16 (d, 1.9, H-2), 6.79 (d, 8.2, H-5), 7.05 (dd, 8.2, 1.9, H-6), 7.62 (d, 15.9, H-7),
6.38 (d, 15.9, H-8), 3.87 (s, MeO-3); 13C-NMR (100 MHz, CD3OD): 93.1 (C-1), 142.5 (C-3), 108.4 (C-4), 72.7 (C5), 78.3 (C-6), 46.9 (C-7), 78.4 (C-8), 59.5 (C-9), 25.0 (C-10), 99.2 (C-1), 74.4 (C-2), 77.4 (C-3), 71.7 (C-4), 75.6
(C-5), 64.5 (C-6), 127.6 (C-1), 117.7 (C-2), 149.3 (C-3), 150.6 (C-4), 116.5 (C-5), 124.2 (C-6), 147.1 (C-7),
115.2 (C-8), 169.1 (C-9), 56.4 (MeO-3). Scrophularia ningpoensis (Scrophulariaceae).12)
6-O-Glucopyranosylharpagoside
C30H40O16: 656.2316; pale brown amorphous powder; [a ]D26 11.6 (c1.0, MeOH); UV (MeOH): 279 (2.35), 222
(2.27), 216 (2.31), 204 (2.37); IR (KBr): 3421, 1701, 1632, 1601, 1516; 1H-NMR (400 MHz, CD3OD): 6.19 (d, 1.2,
H-1), 6.39 (d, 6.4, H-3), 4.93 (dd, 6.4, 1.6, H-4), 3.74 (t, 3.4, H-6), 2.24 (d, 15.1, H-7), 1.99 (dd, 15.4, 4.4, H-7), 2.92
(s, H-9), 1.53 (s, H3-10), 6.63 (d, 7.9, H-1), 3.23 (t, 9.1, H-2), 3.433.46 (m, H-3), 3.38 (t, 7.4, H-4), 3.523.56
(m, H-5), 4.20 (dd, 12.0, 1.8, H-6), 3.89 (dd, 12.0, 6.5, H-6), 4.59 (d, 7.9, H-1), 3.23 (t, 9.1, H-2), 3.403.42 (m,
H-3), 3.38 (t, 7.4, H-4), 3.53 (d, 9.1, H-5), 3.90 (dd, 12.0, 2.3, H-6), 3.68 (dd, 12.0, 5.8, H-6), 7.577.61 (m, H2, 6), 7.367.40 (m, H-3, 5), 7.397.41 (m, H-4), 7.70 (d, 16.0, H-7), 6.50 (d, 16.0, H-8); 13C-NMR
(100 MHz, CD3OD): 94.3 (C-1), 143.8 (C-3), 107.0 (C-4), 73.6 (C-5), 77.7 (C-6), 46.3 (C-7), 88.5 (C-8), 55.4 (C-9),
22.9 (C-10), 99.3 (C-1), 74.4 (C-2), 77.7 (C-3), 71.7 (C-4), 77.7 (C-5), 69.6 (C-6), 104.6 (C-1), 75.4 (C-2),
77.7 (C-3), 71.7 (C-4), 77.7 (C-5), 62.8 (C-6), 136.0 (C-1), 129.2 (C-2, 6), 130.0 (C-3, 5), 131.3 (C-4),
146.0 (C-7), 120.3 (C-8), 168.3 (C-9). Scrophularia ningpoensis (Scrophulariaceae).12)
5-O-b -Glucopyranosylharpagide
C21H34O15: 526.1897; amorphous powder, [a ]D21 33.1 (c0.45, MeOH); 1H-NMR (400 MHz, CD3OD): 5.75 (d, 1.5, H-1),
6.39 (d, 6.6, H-3), 5.15 (d, 6.6, H-4), 3.93 (dd, 3.8, 3.2, H-6), 1.85 (br s, H2-7), 2.76 (d, 1.5, H-9), 1.25 (s, H3-10), 4.71 (d, 7.8,
H-1), 3.88 (dd, 12.0, 2.0, H-6), 3.66 (dd, 12.0, 5.6, H-6), 4.59 (d, 7.8, H-1), 3.78 (dd, 12.6, 2.2, H-6), 3.70 (dd, 12.6, 4.6, H6); 13C-NMR (100 MHz, CD3OD): 93.0 (C-1), 143.6 (C-3), 104.5 (C-4), 80.1 (C-5), 76.7 (C-6), 46.6 (C-7), 78.4 (C-8), 57.2
(C-9), 25.1 (C-10), 99.2 (C-1), 74.8 (C-2), 78.4 (C-3), 71.7 (C-4), 77.1 (C-5), 62.8 (C-6), 97.5 (C-1), 75.2 (C-2), 78.1
(C-3), 70.7 (C-4), 78.0 (C-5), 61.9 (C-6). Clerodendrum chinense (Verbenaceae).13)
Genestifolioside
C17H28O11: 408.1631; white powder; [a ]D25 99.9 (c0.001, MeOH); UV (MeOH): 300.0 (3.9); IR (KBr): 34003200, 1HNMR (500 MHz, CD3OD): 5.43 (d, 7.3, H-1), 6.43 (d, 7.6, H-3), 4.81 (d, 7.6, H-4), 3.70 (d, 1.3, H-6), 5.40 (d, 1.3, H-7), 3.41
(d, 7.3, H-9), 2.13 (s, H3-10), 4.10 (q, 6.8, H-11), 1.32 (t, 6.8, H3-12), 4.71 (d, 8.0, H-1), 3.90 (dd, 8.7, 8.0, H-2), 3.42 (br t,
8.7, H-3), 3.53 (dd, 8.7, 8.7, H-4), 2.9 (m, H-5), 3.32 (dd, 11.7, 8.7, H-6), 3.84 (dd, 11.7, 1.9, H-6); 13C-NMR (125 MHz,
CD3OD): 93.2 (C-1), 142.3 (C-3), 104.3 (C-4), 72.2 (C-5), 83.8 (C-6), 74.9 (C-7), 78.9 (C-8), 49.2 (C-9), 20.1 (C-10), 63.3
(C-11), 14.4 (C-12), 99.2 (C-1), 74.5 (C-2), 77.5 (C-3), 71.4 (C-4), 74.2 (C-5), 62.3 (C-6). Linaria genestifolia (Scrophulariaceae).14)
16.
6,8-Diacetylharpagide
C19H28O12: 448.1580; colorless amorphous powder; [a ]D25 65.0 (c0.5, MeOH); UV (MeOH): 203 (3.5); IR (KBr): 3500,
1734, 1650, 10301010; 1H-NMR (500 MHz, DMSO-d6CDCl3): 5.54 (d, 1.0, H-1), 6.53 (d, 6.6, H-3), 5.0 (dd, 6.6, 1.7, H4), 5.23 (d, 4.5, H-6), 2.20 (d, 15.6, H-7), 2.00 (dd, 15.6, 4.0, H-7), 2.86 (m, H-9), 1.35 (s, H3-10), 1.98 (s, AcO-8), 2.10 (s,
AcO-6), 4.70 (d, 7.6, H-1), 3.28 (m, H-2), 3.60 (m, H-3), 3.39 (m, H-4), 3.52 (m, H-5), 3.94 (dd, 13.0, 1.8, H-6), 3.80 (dd,
13.6, 5.5, H-6); 13C-NMR (125 MHz, DMSO-d6CDCl3): 95.1 (C-1), 144.2 (C-3), 108.0 (C-4), 74.5 (C-5), 79.1 (C-6), 47.6
(C-7), 90.7 (C-8), 55.9 (C-9), 23.5 (C-10), 98.1 (C-1), 77.9 (C-2), 78.8 (C-3), 72.6 (C-4), 77.4 (C-5), 62.8 (C-6), 24.8,
25.2, 170.1, 170.4 (2Ac). Ajuga remota (Labiatae).15)
768
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Vol. 57, No. 8

6,8-Diacetylharpagide-1-O-b -(2,3-di-O-acetylglucoside)
C23H32O14: 532.1791; colorless crystals; mp 174176 C; [a ]D25 92.0 (c1.5, CH2Cl2); UV (MeOH): 210 (2.76); IR
(KBr): 35003200, 1732, 1650, 10251010; 1H-NMR (500 MHz, DMSO-d6CDCl3): 5.56 (d, 1.1, H-1), 6.44 (d,
6.3, H-3), 4.94 (dd, 6.3, 1.3, H-4), 2.30 (d, 15.5, Hb -7), 2.14 (dd, 15.5, 1.2, Ha -7), 2.84 (d, 1.8, H-9), 1.36 (s, H3-10),
2.15 (s, AcO-6), 2.04 (s, AcO-8), 4.60 (d, 7.8, H-1), 5.02 (t, 8.8, H-2), 5.10 (t, 9.0, H-3), 3.50 (m, H-4), 3.55 (m, H5), 4.01 (dd, 12.4, 2.2, H-6), 3.81 (dd, 12.4, 5.4, H-6), 2.01 (s, AcO-2), 1.95 (s, AcO-3); 13C-NMR (125 MHz,
CDCl3DMSO-d6): 95.4 (C-1), 143.7 (C-3), 107.2 (C-4), 73.3 (C-5), 80.0 (C-6), 46.9 (C-7), 89.0 (C-8), 55.2 (C-9),
22.8 (C-10), 98.9 (C-1), 74.0 (C-2), 76.6 (C-3), 71.2 (C-4), 76.9 (C-5), 62.4 (C-6), 24.9, 25.02, 25.4, 169.8,
170.0, 170.1, 171.0 (4Ac). Ajuga remota (Labiatae).15)
Harprocumbide A (6-O-a -D-Galactopyranosylharpagoside)
C30H40O16: 656.2316; white amorphous powder; [a ]D22 16.3 (c0.10, MeOH); 1H-NMR (400 MHz, C5D5N):
6.86 (s, H-1), 6.47 (d, 6.4, H-3), 5.15 (d, 6.4, H-4), 4.66 (d, 4.2, H-6), 2.10 (dd, 14.8, 4.2, H-7), 2.60 (d, 14.8, H-7),
3.60 (s, H-9), 1.70 (s, H3-10), 5.26 (d, 8.0, H-1), 3.99 (t, 8.4, H-2), 4.17 (t, 8.4, H-3), 4.08 (m, H-4), 4.05 (m, H5), 4.52 (dd,10.0, 4.8, H-6), 4.32 (d, 10.0, H-6), 5.54 (d, H-1), 4.57 (m, H-2), 4.65 (d, 10.0, H-3), 4.67 (m, H4), 4.75 (t, 6.0, H-5), 4.47 (d, 5.8, H2-6), 7.50 (m, H-2, 6), 7.25 (m, H-3, 4,5), 7.82 (d, 16.0, H-7), 6.53 (d,
16.0, H-8); 13C-NMR (100 MHz, C5D5N): 95.0 (C-1), 143.0 (C-3), 109.1 (C-4), 74.4 (C-5), 77.6 (C-6), 47.0 (C7), 88.3 (C-8), 55.9 (C-9), 23.7 (C-10), 99.2 (C-1), 75.6 (C-2), 77.8 (C-3), 72.1 (C-4), 79.5 (C-5), 69.1 (C-6),
101.6 (C-1), 71.7 (C-2), 73.1 (C-3), 72.6 (C-4), 73.6 (C-5), 63.8 (C-6), 136.0 (C-1), 130.0 (C-2, 6), 129.5
(C-3, 5), 131.2 (C-4), 145.3 (C-7), 121.1 (C-8), 167.6 (C-9). Harpagophytum procumbens (Pedaliaceae).11)
6-O-E-Cinnamoyl-E-harpagoside
C33H36O12: 624.2206; white amorphous powder; [a ]D25 40.0 (c0.10, MeOH); UV (MeOH): 273 (4.66), 216 (4.50),
203 (4.56); IR (KBr): 3418, 2960, 2929, 1704, 1636, 1450, 1282, 1204, 1076, 1028; 1H-NMR (600 MHz, CD3OD):
6.19 (s, H-1), 6.51 (m, H-3), 5.06 (m, H-4), 4.96 (d, 3.7, H-6), 2.45 (d, 16.0, Ha-7), 2.12 (dd, 16.0, 4.0, Hb-7), 3.09 (s, H9), 1.60 (s, H3-10), 4.65 (d, 7.8, H-1), 3.23 (dd, 9.0, 7.8, H-2), 3.41 (m, H-3), 3.32 (m, H-4), 3.38 (m, H-5), 3.95
(dd, 12.6, 2.4, Ha-6), 3.74 (dd, 12.6, 6.2, Hb-6), 7.38 (d, 7.3, H-2, 6), 7.14 (t, 7.6, H-3, 5), 7.25 (t, 7.3, H-4), 7.63
(d, 16.0, H-7), 6.41 (d, 16.0, H-8), 7.39 (d, 7.2, H-2, 6), 7.20 (t, 7.6, H-3, 5), 7.30 (t, 7.3, H-4), 7.74 (d, 16.0, H7), 6.50 (d, 16.0, H-8); 13C-NMR (150 MHz, CD3OD): 93.0 (C-1), 143.4 (C-3), 104.5 (C-4), 71.7 (C-5), 78.9 (C-6),
42.6 (C-7), 87.4 (C-8), 54.7 (C-9), 20.9 (C-10), 98.9 (C-1), 73.2 (C-2), 76.8 (C-3), 70.4 (C-4), 76.2 (C-5), 61.6 (C6), 133.9 (C-1), 127.8 (C-2, 6), 128.4 (C-3), 129.9 (C-4), 128.5 (C-5), 145.1 (C-7), 117.6 (C-8), 166.5 (C-9),
134.1 (C-1), 127.8 (C-2, 6), 128.4 (C-3), 130.0 (C-4), 128.5 (C-5), 145.3 (C-7), 118.4 (C-8), 166.9 (C-9).
Goldfussia yunnanensis (Acanthaceae).16)
Stachysoside E (3-O-p-Coumaroyl ester of melittoside)
C30H38O17; 670.2108; colorless amorphous powder; [a ]D24 23.6 (c1.06, MeOH); 1H-NMR (400 MHz, CD3OD):
5.61 (d, 3.5, H-1), 6.38 (d, 6.0, H-3), 5.13 (a , 6.0, H-4), 4.39 (m, H-6), 5.80 (m, H-7), 3.35 (overlapped, H-9), 4.20 (m,
H-10), 4.62 (d, 8.0, H-1), 3.28 (overlapped, H-2), 3.203.40 (overlapped, H-3, 4), 3.31 (overlapped, H-5), 3.66 (m,
H-6), 3.88 (br d, H-6), 4.81 (d, 8.0, H-1), 3.47 (dd, 9.5, 8.0, H-2), 5.08 (dd, 9.5, 9.5, H-3), 3.61 (dd, 9.5, 9.5, H-4),
3.43 (m, H-5), 3.75 (dd, 12.5, 5.0, H-6), 3.83 (dd, 12.5, 2.0, H-6), 7.47 (d, 8.5, H-2, 6), 6.89 (d, 8.5, H-3, 5), 7.66
(d, 16.0, H-7), 6.40 (d, 16.0, H-8); 13C-NMR (100 MHz,CD3OD): 94.2 (C-1), 143.5 (C-3), 105.2 (C-4), 80.2 (C-5),
80.0 (C-6), 128.2 (C-7), 147.4 (C-8), 51.7 (C-9), 61.0 (C-10), 98.3 (C-1), 75.0 (C-2), 78.5 (C-3), 71.7 (C-4), 77.3
(C-5), 62.8 (C-6), 99.7 (C-1), 73.5 (C-2), 79.3 (C-3), 69.2 (C-4), 78.0 (C-5), 61.9 (C-6), 127.4 (C-1), 131.1 (C2, 6), 116.9 (C-3, 5), 161.2 (C-4), 146.6 (C-7), 115.6 (C-8), 169.1 (C-9). Stachys lanata (Labiatae).17)
Stachysoside F
5.59 (d, 4.0, H-1), 6.38 (d, 6.5, H-3), 5.14 (d, 6.5, H-4), 4.40 (m, H-6), 5.79 (m, H-7), 3.30 (overlapped, H-9), 4.19 (m,
H-10), 4.61 (d, 7.6, H-1), 3.28 (overlapped, H-2), 3.203.40 (overlapped, H-3, 4), 3.31 (overlapped, H-5), 3.66 (m,
H-6), 3.88 (br d, 12.0, H-6), 4.80 (d, 8.0, H-1), 3.42 (dd, 9.5, 8.0, H-2), 5.07 (dd, 9.5, 9.5, H-3), 3.55 (dd, 9.5, 9.5,
H-4), 3.40 (m, H-5), 3.73 (dd,12.5, 5.0, H-6), 3.82 (dd, 12.5, 2.0, H-6), 7.66 (d, 8.5, H-2, 6), 6.73 (d, 8.5, H-3,
5), 6.86 (d, 13.0, H-7), 5.85 (d, 13.0, H-8); 13C-NMR (67.5 MHz, CD3OD): 94.4 (C-1), 143.7 (C-3), 105.3 (C-4),
80.4 (C-5), 80.1 (C-6), 128.2 (C-7), 147.3 (C-8), 51.7 (C-9), 61.0 (C-10), 98.3 (C-1), 74.9 (C-2), 78.5 (C-3), 71.7
(C-4), 77.3 (C-5), 62.8 (C-6), 99.7 (C-1), 73.4 (C-2), 78.7 (C-3), 69.1 (C-4), 78.0 (C-5), 61.9 (C-6), 127.6
(C-1), 133.8 (C-2, 6), 115.9 (C-3, 5), 160.2 (C-4), 144.8 (C-7), 116.9 (C-8), 168.1 (C-9). Stachys lanata
(Labiatae).17)
Stachysoside G
5.46 (d, 5.0, H-1), 6.33 (d, 6.5, H-3), 5.10 (d, 6.5, H-4), 4.42 (m, H-6), 5.77 (m, H-7), 3.30 (overlapped, H-9), 4.12
(dd, 15.0, 1.0, H-10), 4.24 (m, H-10), 4.58 (d, 7.5, H-1), 3.23 (overlapped, H-2), 3.203.40 (overlapped, H-35),
3.61 (m, H-6), 3.85 (dd, 11.5, 1.0, H-6), 4.67 (d, 8.0, H-1), 3.26 (overlapped, H-2), 3.203.40 (overlapped, H-3),
3.29 (overlapped, H-4), 3.59 (m, H-5), 4.23 (dd, 12.0, 5.0, H-6), 4.53 (dd, 12.0, 2.0, H-6), 7.47 (d, 9.0, H-2, 6),
6.82 (d, 9.0, H-3, 5), 7.65 (d, 16.0, H-7), 6.37 (d, 16.0, H-8); 13C-NMR (100 MHz, CD3OD): 95.5 (C-1), 143.8
(C-3), 105.9 (C-4), 81.1 (C-5), 81.2 (C-6), 128.0 (C-7), 147.2 (C-8), 52.2 (C-9), 61.2 (C-10), 99.2 (C-1), 74.9 (C2), 78.1 (C-3), 71.5 (C-4), 77.6 (C-5), 62.8 (C-6), 99.8 (C-1), 75.1 (C-2), 78.5 (C-3), 71.8 (C-4), 75.4 (C-5),
64.8 (C-6), 127.2 (C-1), 131.3 (C-2, 6), 117.0 (C-3, 5), 161.5 (C-4), 146.8 (C-7), 115.3 (C-8), 169.4 (C-9).
Stachys lanata (Labiatae).17)
Stachysoside H
5.19 (d, 7.5, H-1), 6.52 (d, 5.5, H-3), 4.83 (overlapped, H-4), 4.45 (m, H-6), 5.72 (m, H-7), 3.35 (overlapped, H-9), 4.22
(m, H-10), 4.65 (d, 7.5, H-1), 3.23 (dd, 9.0, 7.5, H-2), 3.37 (overlapped, H-3), 3.203.40 (overlapped, H-4), 3.26
(overlapped, H-5), 3.62 (dd, 12.5, 5.0, H-6), 3.84 (dd, 12.5, 2.0, H-6), 4.82 (d, 8.0, H-1), 4.79 (dd, 9.0, 8.0, H-2),
3.64 (dd, 9.0, 9.0, H-3), 3.42 (dd, 9.5, 9.0, H-4), 3.32 (overlapped, H-5), 3.69 (dd, 12.5, 5.0, H-6), 3.84 (dd, 12.5,
2.0, H-6), 7.48 (d, 9.0, H-2, 6), 6.82 (d, 9.0, H-3, 5), 7.68 (d, 16.0, H-7), 6.40 (d, 16.0, H-8); 13C-NMR
61.5 (C-10), 99.7 (C-1), 74.8 (C-2), 78.5 (C-3), 71.6 (C-4), 77.7 (C-5), 62.5 (C-6), 97.9 (C-1), 75.4 (C-2), 76.0
(C-3), 71.5 (C-4), 77.9 (C-5), 62.7 (C-6), 127.2 (C-1), 131.3 (C-2, 6), 116.9 (C-3, 5), 161.4 (C-4), 147.4 (C7), 115.1 (C-8), 168.9 (C-9). Stachys lanata (Labiatae).17)
August 2009
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769
6-O-Vanilloyl-3,4-dihydrocatalpol (Piscroside A)
C23H30O13: 514.1686; amorphous powder; [a ]D25 59.8 (c0.40, MeOH); IR (KBr): 3419, 2925, 1702, 1605, 1516,
1430, 1286, 1221, 1070, 763; 1H-NMR (600 MHz, DMSO-d6): 4.46 (d, 8.7, H-1), 3.74 (m, Ha -3), 3.19 (overlapped,
Hb -3), 1.44 (d, 13.5, Ha -4), 1.58 (m, Hb -4), 1.80 (dd, 13.5, 8.1, H-5), 3.77 (dd, 9.0, 6.6, H-6), 3.18 (d, 9.0, H-7), 2.04
(t, 8.0, H-9), 3.41 (dd, 13.2, 7.3, H-10), 3.81 (overlapped, H-10), 4.55 (d, 7.8, H-1), 3.02 (dd, 7.8, 5.0, H-2), 3.21
(overlapped, H-3), 3.20 (overlapped, H-4), 3.47 (m, H-5), 4.44 (br d, 12.0, H-6), 4.32 (dd, 12.0, 6.3, H-6), 7.44
(d, 1.8, H-2), 6.87 (d, 8.4, H-5), 7.46 (dd, 8.4, 1.8, H-6), 3.81 (s, OMe); 13C-NMR (150 MHz, DMSO-d6): 96.5 (C1), 61.7 (C-3), 23.1 (C-4), 37.2 (C-5), 71.6 (C-6), 60.9 (C-7), 65.2 (C-8), 42.4 (C-9), 59.7 (C-10), 98.3 (C-1), 74.0
(C-2), 76.9 (C-3), 70.9 (C-4), 74.6 (C-5), 64.1 (C-6), 121.3 (C-1), 113.3 (C-2), 148.0 (C-3), 152.2 (C-4),
115.8 (C-5), 124.1 (C-6), 56.3 (OMe), 166.1 (C-7). Picrorhiza scrophulariiflora (Scrophulariaceae).18)
6-O-p-Coumaroyl-3,4-dihydrocatalpol (Piscroside B)
C24H30O12: 510.1737; white amorphous powder; [a ]D25 60.1 (c0.10, MeOH); IR (KBr): 3380, 2918, 1661, 1610,
1580, 1511, 1280, 1241, 1066, 974, 772; 1H-NMR (600 MHz, DMSO-d6): 4.51 (d, 8.7, H-1), 3.75 (m, Ha -3), 3.21
(overlapped, Hb -3), 1.45 (d, 13.5, Ha -4), 1.59 (m, Hb -4), 1.83 (dd, 13.5, 8.1, H-5), 3.79 (dd, 9.0, 6.6, H-6), 3.19 (d,
9.0, H-7), 2.06 (t, 8.0, H-9), 3.46 (dd, 13.2, 7.3, H-10), 3.84 (dd, 13.2, 7.3, H-10), 4.54 (d, 7.8, H-1), 3.03 (dd, 7.8,
5.0, H-2), 3.22 (overlapped, H-3), 3.23 (overlapped, H-4), 3.40 (m, H-5), 4.34 (br d, 12.0, H-6), 4.25 (dd, 12.0,
6.0, H-6), 7.57 (d, 8.5, H-2,6), 6.79 (d, 8.5, H-3, 5), 7.56 (d, 15.9, H-7), 6.40 (d, 15.9, H-8); 13C-NMR
(150 MHz, DMSO-d6): 96.6 (C-1), 61.7 (C-3), 23.1 (C-4), 37.2 (C-5), 71.6 (C-6), 61.0 (C-7), 65.3 (C-8), 42.5 (C-9),
59.7 (C-10), 98.4 (C-1), 73.9 (C-2), 76.9 (C-3), 70.7 (C-4), 74.5 (C-5), 65.3 (C-6), 125.7 (C-1), 131.0 (C-2,
6), 116.5 (C-3, 5), 160.5 (C-4), 145.5 (C-7), 114.7 (C-8), 167.2 (C-9). Picrorhiza scrophulariiflora (Scrophulariaceae).18)
Piscroside B (6-O-E-Cinnamoyl-3b -methoxy-3,4-dihydro-catalpol)
C25H32O12: 524.1893; white amorphous powder; [a ]D20 51.0 (c0.05, MeOH); UV (MeOH): 215, 276; IR (KBr):
3433, 2921, 1712, 1635, 1449, 1388, 1263, 1175; 1H-NMR (300 MHz, CD3OD): 4.90 (d, 8.6, H-1), 4.54 (dd, 9.0,
3.0, H-3), 1.59 (m, Ha-4), 1.81 (br d, 13.9, Hb-4), 2.03 (m, H-5), 3.90 (br d, 9.1, H-6), 3.39 (br s, H-7), 2.37 (t, 8.1, H9), 3.63 (d, 13.1, Ha-10), 4.05 (d, 13.1, Hb-10), 4.75 (d, 7.8, H-1), 3.27 (m, H-2), signal not observed (H-3, 4),
3.53 (m, H-5), 4.44 (dd, 11.9, 5.5, Ha-6), 4.53 (dd, 11.5, 2.4, Hb-6), 7.62 (m, H-2, 6), 7.41 (m, H-3, 5), 7.41 (m,
H-4), 7.72 (d, 16.0, H-7), 6.57 (d, 16.0, H-8 ), 3.45 (s, OMe); 13C-NMR (75 MHz, CD3OD): 95.9 (C-1), 100.5 (C3), 29.7 (C-4), 38.2 (C-5), 75.1 (C-6), 62.3 (C-7), 66.0 (C-8), 43.4 (C-9), 61.5 (C-10), 99.6 (C-1), 74.9 (C-2), 77.8
(C-3), 71.7 (C-4), 76.0 (C-5), 64.4 (C-6), 135.7 (C-1),130.2 (C-2, 6), 129.4 (C-3, 5), 131.7 (C-4), 146.7 (C7), 118.8 (C-8), 168.4 (C-9), 56.6 (OMe). Neopicrorhiza scrophulariiflora (Scrophulariaceae).19)
Pensteminoside
C33H34O13: 638.1999; brown powder; [a ]D 0.06 (c0.35, MeOH); UV (MeOH): 277, 231, 216; IR:
3263, 3207, 2935, 2561, 1725, 1457, 1024, 712, 624; 1H-NMR (500 MHz, acetone-d6): 4.95 (d, 10.0, H1), 6.32 (dd, 6.0, 1.5, H-3), 5.02 (dd, 6.0, 5.0, H-4), 2.24 (dddd, 7.5, 5.0, 3.0, 2.0, H-5), 3.89 (d, 8.5, H6), 3.46 (m, H-7), 2.52 (dd, 10.0, 7.5, H-9), 4.13 (d, 12.5, H-10), 5.07 (d, 12.5, H-10), 4.78 (d, 8.0, H-1),
3.29 (t, 8.5, H-2), 3.46 (m, H-3, 4), 3.58 (m, H-5), 4.45 (dd, 8.5, 3.0, H-6), 7.54 (d, 8.5, H-2, 6),
6.83 (d, 8.5, H-3, 5), 7.63 (d, 16.0, H-7), 6.38 (d, 16.0, H-8), 7.62 (dd, 6.0, 2.5, H-2, 6), 7.40 (m, H3, 4, 5), 7.67 (d, 16.0, H-7), 6.50 (d, 16.0, H-8); 13C-NMR (125 MHz, acetone-d6): 95.3 (C-1),
141.5 (C-3), 103.9 (C-4), 38.9 (C-5), 79.3 (C-6), 62.0 (C-7), 62.8 (C-8), 43.3 (C-9), 63.7 (C-10), 100.0
(C-1), 74.6 (C-2), 77.7 (C-3), 71.0 (C-4), 75.3 (C-5), 64.5 (C-6), 127.1 (C-1), 131.0 (C-2, 6),
116.8 (C-3, 5), 160.6 (C-4), 145.6 (C-7), 115.6 (C-8), 167.6 (C-9), 135.5 (C-1), 129.8 (C-2, 6),
129.1 (C-3, 5), 131.1 (C-4), 145.5 (C-7), 119.1 (C-8), 166.7 (C-9). Penstemon gentianoides
(Plantaginaceae).20)
6-O-(3-O-Benzoyl)-a -L-rhamnopyranosylcatalpol
C28H36O15: 612.2054; isolated as heptaacetate; viscous mass; [a ]D28 17.7 (c0.08, CHCl3); UV: 278, 232; IR
(KBr): 2956, 2925, 1759, 1654, 1637, 1560, 1544, 1510, 1422, 1375, 1080, 1066, 980; 1H-NMR (300 MHz,
CDCl3): 4.77 (d, 9.6, H-1), 6.32 (dd, 6.0, 1.5, H-3), 5.11 (dd, 6.0, 4.8, H-4), 2.57 (m, H-5), 3.95 (dd, 8.5, 1.8, H-6),
3.59 (br s, H-7), 2.65 (dd, 9.6, 8.0, H-9), 3.98 (d, 12.6, H-10), 4.82 (d, 12.6, H-10), 4.97 (d, 8.1, H-1), 5.27 (dd, 9.5,
8.0, H-2), 4.95 (t, 9.6, H-3), 5.22 (t, 9.5, H-4), 3.69 (m, H-5), 4.15 (dd, 12.3, 3.9, H-6), 4.34 (dd, 12.3, 2.4, H6), 4.96 (br s, H-1), 5.34 (dd, 3.5, 1.7, H-2), 5.60 (dd, 9.6, 3.6, H-3), 5.36 (t, 9.6, H-4), 4.08 (dd, 9.8, 6.3, H-5),
1.26 (d, 6.3, H3-6), 8.00 (dd, 8.7, 1.5, H-2, 6), 7.46 (t, 7.8, H-3, 5), 7.58 (tt, 7.5, H-4), 1.89, 2.04, 2.05, 2.07,
2.13, 2.15, 2.19 (each s, 7Ac); 13C-NMR (75 MHz, CDCl3): 94.7 (C-1), 141.5 (C-3), 102.8 (C-4), 35.9 (C-5), 84.2
(C-6), 58.5 (C-7), 67.0 (C-8), 42.3 (C-9), 62.6 (C-10), 97.1 (C-1), 73.0 (C-2), 71.2 (C-3), 68.8 (C-4), 72.8 (C-5),
61.6 (C-6), 97.0 (C-1), 70.7 (C-2), 69.2 (C-3), 72.1 (C-4), 67.7 (C-5), 17.8 (C-6), 129.8 (C-1), 130.2 (C-2,
6), 128.9 (C-3, 5), 133.8 (C-4), 166.1 (C-7), 20.82, 20.92, 21.23, 169.3, 169.5, 170.1, 170.3, 170.5,
170.8, 170.9 (7Ac). Gmelina arborea (Verbenaceae).21)
6-O-(3-O-trans-Cinnamoyl)-a -L-rhamnopyranosylcatalpol
C30H38O15: 638.2210; isolated as heptaacetate; viscous mass; [a ]D28 14.2 (c0.16, CHCl3); UV: 282, 223, 218; IR
(KBr): 2957, 2927, 1750, 1654, 1636, 1560, 1543, 1510, 1426, 1373, 1080, 1044, 982; 1H-NMR (300 MHz, CDCl3):
4.77 (d, 9.6, H-1), 6.32 (dd, 6.0, 1.5, H-3), 5.09 (dd, 6.0, 4.8, H-4), 2.50 (m, H-5), 3.93 (dd, 8.5, 1.8, H-6), 3.57 (br s,
H-7), 2.61 (dd, 9.6, 8.0, H-9), 3.96 (d, 12.6, H-10), 4.80 (d, 12.6, H-10), 4.96 (d, 8.0, H-1), 5.19 (dd, 9.5, 8.0, H-2),
4.96 (t, 9.6, H-3), 5.15 (t, 9.6, H-4), 3.68 (m, H-5), 4.15 (dd, 12.3, 3.9, H-6), 4.32 (dd, 12.3, 2.4, H-6), 4.96 (br s,
H-1), 5.32 (dd, 3.5, 1.7, H-2), 5.42 (dd, 9.6, 3.6, H-3), 5.22 (t, 9.6, H-4), 4.00 (dd, 9.8, 6.3, H-5), 1.24 (d, 6.3, H36), 7.53 (d, 8.2, H-2, 6), 7.40 (t, 8.2, H-3, 5), 7.34 (m, H-4), 7.68 (d, 16.0, H-7), 6.38 (d, 16.0, H-8), 1.93,
1.942, 1.97, 2.03, 2.05, 2.07 (each s, 7Ac); 13C-NMR (75 MHz, CDCl3): 94.7 (C-1), 141.7 (C-3), 102.9 (C-4),
35.9 (C-5), 83.9 (C-6), 58.5 (C-7), 67.0 (C-8), 42.1 (C-9), 62.8 (C-10), 97.1 (C-1), 72.9 (C-2), 71.0 (C-3), 68.7
(C-4), 72.7 (C-5), 61.6 (C-6), 97.1 (C-1), 70.4 (C-2), 69.1 (C-3), 71.4 (C-4), 67.6 (C-5), 17.8 (C-6), 134.5
(C-1), 128.9 (C-2, 6), 129.5 (C-3, 5), 130.9 (C-4), 146.8 (C-7), 117.4 (C-8), 166.2 (C-9), 20.82,
20.93, 21.12, 169.2, 169.4, 170.1, 170.3, 170.4, 170.7, 170.8 (7Ac). Gmelina arborea (Verbenaceae).21)
770
30.
31.
32.
33.
34.
35.
36.
37.
Vol. 57, No. 8

6-O-(3-O-cis-Cinnamoyl)-a -L-rhamnopyranosylcatalpol
C30H38O15: 638.2210; isolated as heptaacetate; viscous mass; [a ]D28 10.4 (c0.14, CHCl3); UV: 285, 225, 215;
IR (KBr): 2957, 2926, 1749, 1653, 1637, 1560, 1543, 1509, 1437, 1373, 1080, 1043, 981; 1H-NMR (300 MHz,
CDCl3): 4.74 (d, 9.6, H-1), 6.31 (dd, 6.0, 1.5, H-3), 5.04 (dd, 6.0, 4.8, H-4), 2.51 (m, H-5), 3.95 (dd, 8.5, 1.5, H-6),
3.54 (br s, H-7), 2.61 (dd, 9.6, 8.0, H-9), 3.94 (d, 12.6, H-10), 4.86 (d, 12.6, H-10), 4.94 (d, 8.1, H-1), 5.21 (dd,
9.5, 8.0, H-2), 4.96 (t, 9.6, H-3), 5.18 (t, 9.5, H-4), 3.69 (m, H-5), 4.21 (dd, 12.3, 3.9, H-6), 4.30 (dd, 12.3, 2.4,
H-6), 4.92 (br s, H-1), 5.31 (dd, 3.5, 1.7, H-2), 5.41 (dd, 9.6, 3.6, H-3), 5.28 (t, 9.6, H-4), 3.98 (dd, 9.8, 6.3, H5), 1.27 (d, 6.3, H3-6), 7.58 (d, 8.2, H-2, 6), 7.38 (t, 8.2, H-3, 5), 7.35 (m, H-4), 7.02 (d, 12.6, H-7), 5.90 (d,
12.6, H-8), 2.01, 2.07, 2.10, 2.16, 2.18, 2.20, 2.23 (each s, 7Ac). Gmelina arborea (Verbenaceae).21)
Myobontioside B
C25H30O14: 554.1635; amorphous powder; [a ]D26 54.6 (c0.28, MeOH); UV (MeOH): 325 (3.95), 235 (3.84), 221
(3.83); IR (film): 3369, 2932, 1702, 1517, 1277, 1164, 1072, 1018; 1H-NMR (400 MHz, CD3OD): 5.22 (d, 8.0, H-1),
6.35 (d, 6.0, H-3), 4.89 (d, 6.0, H-4), 3.95 (d, 1.0, H-6), 3.53 (d, 1.0, H-7), 2.55 (d, 8.0, H-9), 4.13 (d, 13.0, H-10), 3.61
(d, 13.0, H-10), 4.73 (d, 8.0, H-1), 3.28 (dd, 9.0, 8.0, H-2), 3.53 (m, H-3), 3.40 (m, H-4, 5), 4.50 (dd, 12.0, 2.0, H6), 4.43 (dd, 12.0, 6.0, H-6), 7.20 (d, 2.0, H-2), 6.82 (d, 8.0, H-5), 7.09 (dd, 8.0, 2.0, H-6), 7.63 (d, 16.0, H-7), 6.38
(d, 16.0, H-8), 3.90 (s, MeO-3); 13C-NMR (100 MHz, CD3OD): 95.5 (C-1), 142.8 (C-3), 108.0 (C-4), 74.5 (C-5), 78.7
(C-6), 63.4 (C-7), 66.8 (C-8), 51.0 (C-9), 61.6 (C-10), 100.0 (C-1), 74.7 (C-2), 77.6 (C-3), 71.7 (C-4), 76.1 (C-5),
64.1 (C-6), 128.7 (C-1), 112.0 (C-2), 149.2 (C-3), 151.1 (C-4), 116.6 (C-5), 124.3 (C-6), 147.2 (C-7), 115.4 (C8), 168.9 (C-9), 56.6 (MeO-3). Myoporum bontioides (Myoporaceae).23)
Versibirioside
C30H39ClO15: 674.1977; white amorphous powder; [a ]D25 38.3 (c0.014, MeOH); IR (KBr): 3423, 2931, 1702,
1635, 1451, 1355, 1266, 1073, 994, 908, 828, 770, 686; 1H-NMR (300 MHz, CD3OD): 5.66 (d, 2.0, H-1), 5.32 (d,
2.6, H-3), 2.48 (d, 10.0, H-4, 5), 1.75 (d, 10.0, H-4), 4.12 (d, 9.6, H-6), 4.26 (d, 8.2, H-7), 2.57 (d, 10.0, H-9), 3.99
(d, 12.2, H-10), 3.63 (d, 12.2, H-10), 4.70 (d, 7.9, H-1), 3.20 (m, H-2), 3.38 (m, H-3, 5), 3.35 (m, H-4), 3.88 (d,
11.5, H-6), 3.69 (d, 11.5, H-6), 4.96 (d, 1.7, H-1), 4.10 (m, H-2), 6.06 (dd, 9.5, 3.3, H-3), 3.71 (m, H-4, 5),
1.31 (s, H3-6), 7.62 (m, H-2, 6), 7.41 (m, H-3, 4, 5), 7.78 (d, 16.0, H-7), 6.62 (d, 16.0, H-8); 13C-NMR
62.3 (C-10), 99.1 (C-1), 74.8 (C-2), 78.3 (C-3), 71.7 (C-4), 78.3 (C-5), 62.8 (C-6), 102.7 (C-1), 70.1 (C-2),
75.6 (C-3), 71.2 (C-4), 70.8 (C-5), 18.2 (C-6), 131.6 (C-1), 129.3 (C-2, 6), 130.1 (C-3, 5), 135.9 (C-4),
146.6 (C-7), 119.2 (C-8), 168.4 (C-9). Veronica sibirica.24)
Kankanoside B
C15H24O10: 364.1369; amorphous powder; [a ]D26 118.7 (c0.50, MeOH); IR (KBr): 3410, 1647, 1085; 1H-NMR
(500 MHz, CD3OD): 5.49 (d, 6.4, H-1), 6.22 (dd, 6.1, 1.8, H-3), 4.95 (dd, 6.1, 4.0, H-4), 2.83 (m, H-5), 1.40 (ddd, 13.5, 7.3,
5.2, Ha -6), 2.52 (ddd, 13.5, 9.2, 7.0, Hb -6), 4.02 (dd, 7.0, 5.2, H-7), 2.21 (dd, 8.6, 6.4 , H-9), 3.85 (d, 11.9, H-10), 3.99 (d,
11.9, H-10), 4.72 (d, 7.9, H-1), 3.20 (dd, 9.2, 7.9, H-2), 3.38 (dd, 9.2, 8.9, H-3), 3.27 (m, H-4), 3.28 (m, H-5), 3.65 (dd,
11.9, 5.8, H-6), 3.88 (dd, 11.9, 1.5, H-6), 13C-NMR (125 MHz, CD3OD): 94.1 (C-1), 139.9 (C-3), 108.9 (C-4) 30.8 (C-5),
40.6 (C-6), 80.0 (C-7), 84.1 (C-8), 50.5 (C-9), 64.6 (C-10), 99.8 (C-1), 74.9 (C-2), 78.0 (C-3), 71.8 (C-4), 78.3 (C-5),
62.9 (C-6). Cistanche tubulosa (Orobanchaceae).25)
Kankanoside C
C15H25ClO10: 400.1136; amorphous powder; [a ]D26 34.0 (c1.00, MeOH); IR (KBr): 3410, 2964, 1159, 1078; 1H-NMR
(500 MHz, CD3OD): 5.48 (d, 2.5, H-1), 5.10 (br d, ca. 3.0, H-3), 1.70 (br dd, ca. 13.0, 3.0, H-4), 2.70 (br dd, ca. 13.0, 6.0,
H-4), 2.61 (m, H-5), 1.68 (br d, ca. 13.0, Ha -6), 2.44 (m, Hb -6), 3.94 (br s, H-7), 2.47 (dd, 7.9, 2.5, H-9), 4.01 (d, 11.3, H10), 4.04 (d, 11.3, H-10), 4.60 (d, 8.0, H-1), 3.17 (dd, 9.2, 8.0, H-2), 3.36 (dd, 9.2, 8.9, H-3), 3.27 (m, H-4), 3.29 (m, H5), 3.65 (dd, 12.2, 5.8, H-6), 3.88 (dd, 12.2, 1.8, H-6); 13C-NMR (125 MHz, CD3OD): 93.3 (C-1), 96.1 (C-3), 34.7 (C-4),
28.5 (C-5), 38.2 (C-6), 82.0 (C-7), 83.0 (C-8), 50.4 (C-9), 65.1 (C-10), 99.0 (C-1), 74.8 (C-2), 78.2 (C-3), 71.8 (C-4),
78.3 (C-5), 62.9 (C-6). Cistanche tubulosa (Orobanchaceae).25)
Stereospermoside (6-O-trans-p-Coumaroyl-decinnamoyl globularimin)
C24H30O13: 526.1686; amorphous powder; [a ]D24 90.8 (c1.74, MeOH); IR (KBr): 3427, 2927, 1672, 1605, 832; 1HNMR (400 MHz, CD3OD): 5.50 (d, 4.4, H-1), 6.22 (dd, 6.1, 1.8, H-3), 5.19 (dd, 6.1, 3.4, H-4), 2.71 (m, H-5), 4.71 (dd, 5.6,
5.4, H-6), 4.09 (d, 5.6, H-7), 2.45 (dd, 9.8, 4.4, H-9), 3.98 (d, 12.0, H-10), 3.78 (d, 12.0, H-10), 4.62 (d, 7.8, H-1), 3.16 (dd,
8.8, 7.8, H-2), 3.22 (dd, 9.0, 8.8, H-3), 3.26 (dd, 9.0, 8.0, H-4), 3.27 (m, H-5), 3.83 (br d, 11.7, H-6), 3.62 (dd, 11.7, 3.9,
H-6), 7.41 (d, 8.8, H-2, 6), 6.76 (d, 8.8, H-3, 5), 7.60 (d, 15.9, H-7), 6.32 (d, 15.9, H-8); 13C-NMR (100 MHz,
CD3OD): 93.0 (C-1), 140.8 (C-3), 106.0 (C-4), 36.5 (C-5), 85.8 (C-6), 84.3 (C-7), 80.7 (C-8), 48.3 (C-9), 64.3 (C-10), 99.5
(C-1), 74.7 (C-2), 77.9 (C-3), 71.6 (C-4), 78.1 (C-5), 62.8 (C-6), 127.1 (C-1), 131.2 (C-2, 6), 116.8 (C-3, 5), 161.3
(C-4), 146.9 (C-7), 115.0 (C-8), 169.1 (C-9). Stereospermum cylindricum (Bignoniaceae).26)
Myobontioside A
C15H2335ClO9: 382.1030; amorphous powder; [a ]D23 90.7 (c0.14, MeOH); IR (film): 3362, 2927, 1655, 1514, 1229, 1074,
1050, 1010; 1H-NMR (400 MHz, CD3OD): 5.44 (d, 4.0, H-1), 6.22 (dd, 6.0, 2.0, H-3), 4.94 (dd, 6.0, 3.0, H-4), 2.84 (dd, 9.0, 3.0,
H-5), 3.96 (m, H-6), 2.34 (dd, 14.0, 6.0, H-7), 1.81 (dd, 14.0, 4.0, H-7), 2.64 (dd, 9.0, 4.0, H-9), 3.83 (d, 12.0, H-10), 3.74 (dd,
12.0, H-10), 4.65 (d, 8.0, H-1), 3.21 (dd, 9.0, 8.0, H-2), 3.38 (m, H-3), 3.29 (m, H-4, 5), 3.90 (dd, 12.0, 2.0, H-6), 3.65 (dd,
12.0, 6.0, H-6); 13C-NMR (100 MHz, CD3OD): 93.3 (C-1), 140.9 (C-3), 105.7 (C-4), 42.9 (C-5), 77.7 (C-6), 46.2 (C-7), 81.8 (C8), 52.7 (C-9), 52.9 (C-10), 99.7 (C-1), 74.9 (C-2), 78.1 (C-3), 71.9 (C-4), 78.4 (C-5), 63.0 (C-6). Myoporum bontioides
(Myoporaceae).23)
Piscroside A (7-Deoxy-7-a -Cl-pikuroside)
C23H29O13Cl: 548.1296; white amorphous powder; [a ]D20 83.2 (c0.06, MeOH); UV (MeOH): 205, 218, 263, 291; IR
(KBr): 3430, 1695, 1604, 1460, 1380, 1283, 1155; 1H-NMR (300 MHz, CD3OD): 5.61 (d, 2.2, H-1), 5.27 (d, 2.8, H-3),
2.07 (dd, 13.4, 3.2, Ha-4), 2.31 (dd, 13.4, 8.6, Hb-4), 2.33 (ddd, 9.5, 7.9, 2.5, H-5), 5.06 (dd, 8.2, 2.6, H-6), 4.46 (dd, 8.2,1.0,
H-7), 2.59 (br d, 9.5, H-9), 3.64 (dd, 12.2, 1.3, Ha-10), 4.00 (dd, 12.2, 1.0, Hb-10), 4.63 (d, 7.9, H-1), 3.08 (dd, 8.0, 8.9,H2), 3.30 (t, 8.8, H-3), signal not observed (H-4), 3.28 (m, H-5), 3.60 (dd, 12.0, 2.2, Ha-6), 3.81 (m, Hb-6), 7.49 (d, 1.8,
H-2), 6.80 (d, 8.2, H-5), 7.52 (dd, 8.2, 1.8, H-6), 3.84 (s, OMe); 13C-NMR (75 MHz, CD3OD): 93.2 (C-1), 96.0 (C-3),
34.5 (C-4), 34.9 (C-5), 88.0 (C-6), 70.5 (C-7), 80.0 (C-8), signal not observed (C-9), 62.2 (C-10), 99.0 (C-1), 74.8 (C-2),
78.2 (C-3), 71.7 (C-4), 78.2 (C-5), 62.8 (C-6), 122.1 (C-1), 113.8 (C-2), 149.0 (C-3), 153.4 (C-4), 116.2 (C-5),
125.4 (C-6), 167.9 (C-7), 56.6 (OMe). Neopicrorhiza scrophulariiflora (Scrophulariaceae).19)
August 2009
38.
771
Picroroside A
C24H30O12: 510.1737; colorless amorphous powder; [a ]D24 56.3 (c1.12, MeOH); UV (MeOH): 277 (4.32),
217 (4.21); IR (KBr): 3434, 1701, 1636; 1H-NMR (800 MHz, CD3OD): 5.58 (d, 1.8, H-1), 5.27 (d, 3.3, H-3),
1.67 (dd, 13.8, 3.3, Ha -4), 2.43 (dd, 13.8, 8.3, Hb -4), 2.28 (ddd, 8.7, 8.3, 2.8, H-5), 4.01 (dd, 8.2, 2.8, H-6), 4.04
(dd, 8.2, 1.4, H-7), 2.56 (br d, 10.1, H-9), 3.95 (dd, 11.9, 1.4, H-10), 3.57 (dd, 11.9, 1.8, H-10), 4.72 (d, 7.8, H1), 3.21 (dd, 9.1, 7.8, H-2), 3.38 (m, H-3), 3.40 (m, H-4), 3.55 (m, H-5), 4.52 (dd, 11.9, 1.8, H-6), 4.33 (dd,
11.9, 5.5, H-6), 7.61 (overlapped, H-2, 6), 7.40 (overlapped, H-3, 4, 5), 7.70 (d, 16.1, H-7), 6.58 (d, 16.1,
H-8); 13C-NMR (200 MHz, CD3OD): 93.5 (C-1), 95.9 (C-3), 34.8 (C-4), 35.9 (C-5), 84.5 (C-6), 74.7 (C-7),
79.9 (C-8), 48.0 (C-9), 62.2 (C-10), 99.1 (C-1), 74.6 (C-2), 78.0 (C-3), 71.6 (C-4), 75.6 (C-5), 64.8 (C-6),
135.7 (C-1), 129.3 (C-2, 6), 130.0 (C-3, 5), 131.6 (C-4), 146.4 (C-7), 118.6 (C-8), 168.5 (C-9). Neopicrorhiza scrophulariiflora (Scrophulariaceae).27)
39.
Picroroside B
C32H36O15: 660.2054; colorless amorphous powder; [a ]D24 46.7 (c0.15, MeOH); UV (MeOH): 269
(4.52), 217 (4.62); IR (film): 3428, 1635; 1H-NMR (500 MHz, CD3OD): 5.60 (d, 2.1, H-1), 5.33 (d, 3.3, H3), 1.76 (dd, 13.8, 3.3, Ha -4), 2.50 (m, Hb -4), 2.33 (m, H-5), 4.13 (dd, 6.9, 2.9, H-6), 5.38 (d, 6.9, H-7), 2.74
(br d, 10.2, H-9), 3.91 (d, 12.0, H-10), 3.63 (d, 12.0, H-10), 4.74 (d, 8.0, H-1), 3.23 (m, H-2), 3.40 (m, H3), 3.41 (m, H-4), 3.57 (m, H-5), 4.53 (dd, 12.0, 2.1, H-6), 4.34 (dd, 12.0, 5.5, H-6), 7.62 (overlapped,
H-2, 6), 7.39 (overlapped, H-3, 5), 7.38 (overlapped, H-4), 7.72 (d, 16.0, H-7), 6.59 (d, 16.0, H-8),
7.59 (d, 2.1, H-2), 6.85 (d, 8.2, H-5), 7.63 (dd, 8.2, 2.1, H-6), 3.89 (s, MeO-3); 13C-NMR (125 MHz,
CD3OD): 93.5 (C-1), 96.0 (C-3), 34.8 (C-4), 35.0 (C-5), 83.1 (C-6), 87.4 (C-7), 80.1 (C-8), 47.5 (C-9), 62.0
(C-10), 99.0 (C-1), 74.7 (C-2), 78.0 (C-3), 71.6 (C-4), 75.5 (C-5), 64.7 (C-6), 135.7 (C-1), 129.3 (C2, 6), 130.0 (C-3, 5), 131.5 (C-4), 146.6 (C-7), 118.6 (C-8), 168.5 (C-9), 122.1 (C-1), 113.7 (C-2),
148.9 (C-3), 153.4 (C-4), 116.0 (C-5), 125.3 (C-6), 168.1 (C-7), 56.4 (MeO-3). Neopicrorhiza scrophulariiflora (Scrophulariaceae).27)
40.
Picroroside C
(4.81), 217 (4.79); IR (film): 3380, 1705, 1636; 1H-NMR (500 MHz, CD3OD): 5.59 (d, 2.1, H-1), 5.31
(d, 3.5, H-3), 1.73 (dd, 13.8, 3.5, Ha -4), 2.48 (dd, 13.8, 9.0, Hb -4), 2.31 (ddd, 9.4, 9.0, 2.9, H-5), 4.09
(dd, 6.9, 2.9, H-6), 5.33 (d, 6.9, H-7), 2.71 (br d, 10.0, H-9), 3.88 (d, 12.1, H-10), 3.60 (dd, 12.1, 1.2, H10), 4.74 (d, 8.0, H-1), 3.23 (dd, 9.2, 8.0, H-2), 3.39 (m, H-3), 3.41 (m, H-4), 3.56 (m, H-5), 4.53
(dd, 12.0, 2.3, H-6), 4.34 (dd, 12.0, 5.7, H-6), 7.62 (overlapped, H-2, 6, 2, 6), 7.42 (overlapped, H3, 5, 3, 5), 7.39 (overlapped, H-4, 4 ), 7.72 (d, 16.0, H-7), 6.59 (d, 16.0, H-8), 7.76 (d, 16.0, H7), 6.63 (d, 16.0, H-8); 13C-NMR (125 MHz, CD3OD): 93.3 (C-1), 95.9 (C-3), 34.8 (C-4, 5), 82.8 (C6), 87.0 (C-7), 79.7 (C-8), 47.3 (C-9), 61.8 (C-10), 98.9 (C-1), 74.6 (C-2), 77.9 (C-3), 71.4 (C-4),
75.5 (C-5), 64.6 (C-6), 135.6 (C-1, 1), 129.2 (C-2, 6, 2, 6), 129.9 (C-3, 5, 3, 5), 131.4 (C-4,
4), 146.5 (C-7), 118.5 (C-8, 8), 146.7 (C-7) 168.5 (C-9, 9). Neopicrorhiza scrophulariiflora
(Scrophulariaceae).27)
41.
Scutelloside
C15H24O11: 380.1318; amorphous powder; [a ]D20 3.4 (c0.22, MeOH); UV (MeOH): 264.0 sh (0.73); IR (film); 3352,
2914; 1H-NMR (400 MHz, CD3OD): 5.63 (d, 1.6, H-1), 5.27 (d, 2.7, H-3), 2.44 (dd, 13.4, 7.8, H-4), 1.67 (dd, 13.4, 2.7, H4), 2.30 (ddd, 9.5, 7.8, 2.6, H-5), 4.03 (dd, 7.4, 2.6, H-6), 4.04 (dd, 7.4, 0.9, H-7), 2.53 (dd, 9.5, 1.6, H-9), 3.98 (d, 12.4, H10), 3.60 (d, 12.4, H-10), 4.68 (d, 7.8, H-1), 3.18 (dd, 8.6, 7.8, H-2), 3.193.40 (m, H-3, 4, 5), 3.87 (d, 12.4, H-6),
3.66 (d, 12.4, H-6); 13C-NMR (100 MHz, CD3OD): 93.6 (C-1), 96.0 (C-3), 35.3 (C-4), 35.7 (C-5), 86.0 (C-6), 74.7 (C-7),
79.9 (C-8), 48.0 (C-9), 62.0 (C-10), 99.1 (C-1), 75.1 (C-2), 78.3 (C-3), 72.0 (C-4), 78.1 (C-5), 62.9 (C-6). Scutellaria
albida ssp. albida (Lamiaceae).28)
Group 3a (Iridoid glycosides with 10-carbon skeleton, sugar at C-1)
42.
Kankanoside A
C16H26O8: 346.1627; amorphous powder; [a ]D25 107.4 (c0.30, MeOH); IR (KBr): 3410, 2964, 1647, 1076; 1H-NMR
(500 MHz, CD3OD): 5.33 (d, 2.7, H-1), 5.95 (br s, H-3), 2.71 (m, H-5), 1.49 (m, Ha -6), 2.02 (m, Hb -6), 1.67 (m, Ha -7),
1.64 (m, Hb -7), 2.21 (dd, 7.5, 2.7, H-9), 1.31 (s, H3-10), 1.51 (br s, H3-11), 4.62 (d, 7.9, H-1), 3.18 (dd, 8.5, 7.9, H-2),
3.36 (dd, 8.9, 8.5, H-3), 3.26 (dd, 9.5, 8.9, H-4), 3.28 (m, H-5), 3.65 (dd, 11.9, 5.8, H-6), 3.89 (dd, 11.9, 1.9, H-6); 13CNMR (125 MHz, CD3OD): 94.1 (C-1), 134.6 (C-3), 115.0 (C-4), 36.2 (C-5), 28.2 (C-6), 41.4 (C-7), 80.2 (C-8), 53.3 (C-9),
24.6 (C-10), 16.2 (C-11), 99.4 (C-1), 74.9 (C-2), 78.1 (C-3), 71.8 (C-4), 78.2 (C-5), 62.9 (C-6). Cistanche tubulosa
(Orobanchaceae).25)
43.
44.
Gardaloside
C16H22O9: 358.1263; pale yellowish oil; [a ]D23 69.6 (c0.18, MeOH); UV (MeOH): 244 (3.90); IR (KBr); 3367, 2927,
1626, 1410, 1242, 1157; 1H-NMR (500 MHz, CD3OD): 5.65 (d, 3.8, H-1), 7.36 (s, H-3), 3.18 (overlapped, H-5), 2.16 (ddd,
12.6, 6.3, 4.4, H-6), 1.86 (ddd, 12.6, 7.2, 7.2, H-6), 4.31 (overlapped, H-7), 3.05 (overlapped, H-9), 5.35 (s, H2-10) , 9.19 (s,
H-11), 4.67 (d, 7.9, H-1), 3.18 (overlapped, H-2), 3.25 (overlapped, H-3), 3.26 (overlapped, H-4), 3.32 (overlapped, H5), 3.90 (dd, 11.7, 5.3, H-6), 3.63 (overlapped, H-6); 13C-NMR (125 MHz, CD3OD): 97.7 (C-1), 164.5 (C-3), 124.1 (C4), 29.5 (C-5), 39.0 (C-6), 73.9 (C-7), 152.4 (C-8), 44.8 (C-9), 112.8 (C-10), 193.0 (C-11), 100.1 (C-1), 74.7 (C-2), 78.0
(C-3), 71.6 (C-4), 78.5 (C-5), 62.8 (C-6). Gardenia jasminoides (Rubiaceae).29)
6-O-E-p-Coumaroyl-8-epi-loganic acid
C25H30O12: 522.1737; yellowish oil; [a ]D20 50.7 (c0.15, MeOH); UV (MeOH): 298.0 sh (3.53), 309.0
(4.03); IR (film); 3352, 2914, 1644, 1607; 1H-NMR (400 MHz, CD3OD): 5.28 (d, 5.0, H-1), 7.29 (s, H-3),
3.03 (m, H-5), 1.90 (m, H-6), 1.78 (m, H-6), 3.78 (m, H-7), 2.05 (m, H-8), 2.46 (m, H-9), 1.02 (d, 7.4, H3-10),
4.68 (d, 8.2, H-1), 3.24 (dd, 8.0, 7.9, H-2), 3.403.34 (m, H-3, 4), 3.55 (m, H-5), 4.50 (dd, 12.1, 2.7, H6), 4.39 (dd, 12.0, 6.2, H-6), 7.46 (d, 8.6, H-2, 6), 6.80 (d, 8.5, H-3, 5), 7.64 (d, 16.4, H-7), 6.36 (d, 16.4,
H-8); 13C-NMR (100 MHz, CD3OD): 95.6 (C-1), 150.4 (C-3), 115.6 (C-4), 32.2 (C-5), 41.5 (C-6), 79.2 (C7), 45.4 (C-8), 43.2 (C-9) 14.4 (C-10), 172.7 (C-11), 99.9 (C-1), 74.8 (C-2), 77.9 (C-3), 71.7 (C-4), 75.7
(C-5), 64.4 (C-6), 127.1 (C-1), 131.2 (C-2, 6), 116.7 (C-3, 5), 161.8 (C-4), 146.9 (C-7), 114.9 (C-8),
169.8 (C-9). Scutellaria albida ssp. albida (Lamiaceae).28)
772
45.
46.
47.
48.
49.
50.
51.
Vol. 57, No. 8

10-(E)-p-Coumaroyl-6,7-dihydromonotropein
C25H30O13: 538.1686; colorless solid; [a ]D25 44.4 (c0.20, MeOH); UV (MeOHH2O): 310, 230, 215; IR (Ge
ATR): 3308, 1684, 1634, 1604, 1515, 1169, 1074; 1H-NMR (360 MHz, CD3OD): 5.51 (d, 5.3, H-1), 7.49 (d, 1.4,
H-3), 2.93 (ddddd, 15.2, 9.2, 1.7, 1.4, 0.5, H-5), 1.70 (m, H-6), 2.17 (m, H-6), 1.841.71 (m, H2-7), 2.32 (dd, 9.2,
5.3, H-9), 4.18 (d, 11.3, H-10), 4.26 (d, 11.3, H-10), 4.73 (d, 7.9, H-1), 3.24 (dd, 9.0, 7.9, H-2), 3.33 (overlapped,
H-3), 3.35 (t, 9.0, H-4), 3.34 (overlapped, H-5), 3.66 (dd, 11.8, 5.2, H-6), 3.85 (dd, 11.8, 1.6, H-6), 7.49
(br ddd, 8.7, 2.9, 2.0, H-2, 6), 6.80 (br ddd, 8.7, 2.9, 2.0, H-3, 5), 7.67 (d, 15.9, H-7), 6.39 (d, 15.9, H-8); 13CNMR (90 MHz, CD3OD): 96.1 (C-1), 153.3 (C-3), 112.5 (C-4), 35.2 (C-5), 31.6 (C-6), 37.5 (C-7), 81.7 (C-8),
46.9 (C-9), 70.9 (C-10), 170.7 (C-11), 100.9 (C-1), 74.6 (C-2), 77.9 (C-3), 71.2 (C-4), 78.4 (C-5), 62.5 (C-6),
127.1 (C-1), 131.3 (C-2, 6), 116.9 (C-3, 5), 161.4 (C-4), 147.0 (C-7), 114.9 (C-8 ), 169.2 (C-9). Vaccinium
macrocarpon (Ericaceae).30)
10-(Z)-p-Coumaroyl-6,7-dihydromonotropein
C25H30O13: 538.1686; colorless amorphous solid; [a ]D25 37.8 (c0.10, MeOH); UV (MeOHH2O): 314,
231, 215; IR (Ge ATR): 3308, 1695, 1684, 1558, 1507, 1457, 1188, 1160, 1071; 1H-NMR (360 MHz,
CD3OD): 5.47 (d, 5.4, H-1), 7.46 (d, 1.4, H-3), 2.84 (ddddd, 15.2, 9.4, 2.0, 1.4, 0.5, H-5), 1.63 (m, H-6), 2.11
(m, H-6), 1.751.65 (m, H2-7), 2.22 (dd, 9.4, 5.4, H-9), 4.11 (d, 11.2, H-10),4.18 (d, 11.2, H-10), 4.71 (d, 7.9,
H-1), 3.24 (dd, 9.0, 7.9, H-2), 3.33 (overlapped, H-3, 5), 3.35 (t, 9.0, H-4), 3.67 (dd, 11.8, 5.1, H-6), 3.86
(dd, 11.8, 1.4, H-6), 7.62 (br ddd, 8.7, 3.0, 2.1, H-2, 6), 6.75 (br ddd, 8.7, 3.0, 2.1, H-3, 5), 6.91 (d, 12.6, H7), 5.86 (d, 12.6, H-8); 13C-NMR (90 MHz, D2O): 95.1 (C-1), 152.5 (C-3), 111.6 (C-4), 32.4 (C-5), 29.7 (C6), 35.6 (C-7), 80.4 (C-8), 45.7 (C-9), 69.6 (C-10), 171.3 (C-11), 98.9 (C-1), 72.7 (C-2), 75.7 (C-3), 70.1 (C4), 76.4 (C-5), 60.8 (C-6), 127.3 (C-1), 131.5 (C-2, 6), 115.3 (C-3, 5), 156.8 (C-4), 144.3 (C-7), 116.9
(C-8), 169.2 (C-9). Vaccinium macrocarpon (Ericaceae).30)
10-O-(E)-p-Coumaroylscandoside
C25H28O13: 536.1529; amorphous powder; [a ]D23 65.4 (c0.54, MeOH); UV (MeOH): 314 (4.01), 303 (3.56),
242 (3.87); IR (KBr): 3407, 2924, 1682, 1632, 1604, 1516, 1205, 1142, 1076, 839; 1H-NMR (500 MHz, C5D5N):
5.37 (d, 8.0, H-1), 7.89 (s, H-3), 3.39 (dd, 7.0, 6.5, H-5), 4.92 (br s, H-6), 6.04 (s, H-7), 3.12 (dd, 8.0, 7.0, H-9),
5.33 (d, 14.5, H-10), 5.06 (d, 14.5, H-10), 5.40 (d, 7.5, H-1), 4.12 (dd, 9.0, 7.5, H-2), 4.28 (dd, 9.0, 8.5, H-3),
4.26 (m, H-4), 3.97 (m, H-5), 4.48 (dd, 12.0, 2.0, H-6), 4.33 (dd, 12.0, 5.5, H-6), 7.58 (d, 8.5, H-2, 6), 7.17 (d,
8.5, H-3, 5), 7.91 (d, 16.0, H-7), 6.57 (d, 16.0, H-8); 13C-NMR (125 MHz, C5D5N): 98.9 (C-1), 152.5 (C-3),
111.7 (C-4), 46.3 (C-5), 82.1 (C-6), 133.7 (C-7), 140.6 (C-8), 47.2 (C-9), 62.3 (C-10), 173.0 (C-11), 101.0 (C-1),
74.8 (C-2), 78.3 (C-3), 71.3 (C-4), 78.8 (C-5), 62.6 (C-6), 125.9 (C-1), 130.8 (C-2, 6), 116.8 (C-3, 5),
161.5 (C-4), 145.6 (C-7), 114.7 (C-8), 167.0 (C-9). Craibiodendron henryi (Ericaceae).31)
10-O-(Z)-p-Coumaroylscandoside
242 (3.99); IR (KBr): 3407, 2924, 1682, 1633, 1604, 1516, 1205, 1142, 1076, 839; 1H-NMR (500 MHz, C5D5N):
5.35 (d, 8.0, H-1), 7.87 (s, H-3), 3.35 (dd, 7.0, 6.5, H-5), 4.89 (br s, H-6), 6.04 (s, H-7), 3.08 (dd, 8.0, 7.0, H-9),
5.23 (d, 14.5, H-10), 5.01 (d, 14.5, H-10), 5.39 (d, 7.5, H-1), 4.10 (dd, 9.0, 7.5, H-2), 4.27 (t, 9.0, H-3), 4.21 (t,
9.0, H-4), 3.97 (m, H-5), 4.48 (dd, 12.0, 2.5, H-6), 4.31 (dd, 12.0, 5.5, H-6), 8.03 (d, 8.5, H-2, 6), 7.16 (d, 8.5,
H-3, 5), 6.92 (d, 13.0, H-7), 5.93 (d, 13.0, H-8); 13C-NMR (125 MHz, C5D5N): 98.8 (C-1), 152.6 (C-3), 111.8
(C-4), 46.4 (C-5), 82.1 (C-6), 132.9 (C-7), 140.3 (C-8), 47.3 (C-9), 62.7 (C-10), 173.0 (C-11), 100.9 (C-1), 74.9
(C-2), 78.3 (C-3), 71.5 (C-4), 78.9 (C-5), 62.3 (C-6), 126.4 (C-1), 133.8 (C-2, 6), 116.0 (C-3, 5), 160.7 (C4), 144.7 (C-7), 115.6 (C-8), 166.2 (C-9). Craibiodendron henryi (Ericaceae).31)
10-O-(E)-p-Coumaroyl-desacetylasperulosidic acid
236 (3.70); IR (KBr): 3410, 2929, 1682, 1633, 1604, 1516, 1203, 1076, 839; 1H-NMR (500 MHz, C5D5N): 5.85 (d,
8.5, H-1), 8.15 (d, 1.0, H-3), 3.47 (dd, 8.0, 5.5, H-5), 5.47 (dd, 5.5, 2.0, H-6), 6.34 (s, H-7), 2.88 (dd, 8.5, 8.0, H-9),
5.20 (d, 15.0, H-10), 5.60 (d, 15.0, H-10), 5.34 (d, 7.5, H-1), 4.16 (dd, 8.5, 7.5, H-2), 4.25 (dd, 9.0, 8.5, H-3),
4.31 (m, H-4), 3.82 (m, H-5), 4.36 (m, H-6), 4.30 (m, H-6), 7.56 (d, 9.0, H-2, 6), 7.16 (d, 9.0, H-3, 5), 7.90
(d, 16.0, H-7), 6.60 (d, 16.0, H-8); 13C-NMR (125 MHz, C5D5N): 101.7 (C-1), 153.8 (C-3), 109.2 (C-4), 42.7 (C5), 74.5 (C-6), 132.3 (C-7), 144.5 (C-8), 46.1 (C-9), 63.0 (C-10), 169.8 (C-11), 101.6 (C-1), 74.9 (C-2), 78.3 (C3), 71.2 (C-4), 78.3 (C-5), 62.5 (C-6), 126.0 (C-1), 130.8 (C-2, 6), 116.8 (C-3, 5), 161.6 (C-4), 145.6 (C7), 114.8 (C-8), 167.1 (C-9). Craibiodendron henryi (Ericaceae).31)
10-O-(Z)-p-Coumaroyl-desacetylasperulosidic acid
237 (4.00); IR (KBr): 3406, 2927, 1685, 1633, 1604, 1516, 1203, 1140, 839; 1H-NMR (500 MHz, C5D5N): 5.82 (d,
8.5, H-1), 8.13 (s, H-3), 3.41 (dd, 8.0, 5.5, H-5), 5.45 (dd, 5.5, 2.0, H-6), 6.29 (s, H-7), 2.83 (dd, 8.5, 8.0, H-9),
5.42 (d, 14.0, H-10), 5.16 (d, 14.0, H-10), 5.31 (d, 7.5, H-1), 4.13 (dd, 8.5, 7.5, H-2), 4.26 (dd, 9.0, 8.5, H-3),
4.29 (m, H-4), 3.80 (m, H-5), 4.35 (m, H-6), 4.25 (m, H-6), 8.04 (d, 8.5, H-2, 6), 7.15 (d, 8.5, H-3, 5), 6.92
(d, 13.0, H-7), 5.94 (d, 13.0, H-8); 13C-NMR (125 MHz, C5D5N): 101.5 (C-1), 153.7 (C-3), 109.3 (C-4), 42.6 (C5), 74.5 (C-6), 132.8 (C-7), 144.2 (C-8), 46.1 (C-9), 62.9 (C-10), 169.7 (C-11), 101.4 (C-1), 74.9 (C-2), 78.2 (C3), 71.4 (C-4), 78.3 (C-5), 62.5 (C-6), 126.4 (C-1), 133.8 (C-2, 6), 116.0 (C-3, 5), 160.7 (C-4), 144.6 (C7), 115.7 (C-8), 166.3 (C-9). Craibiodendron henryi (Ericaceae).31)
Hedycoryside C
C23H26O11: 478.1475; amorphous powder; [a ]D24 11.6 (c0.50, MeOH); UV (MeOH): 229 (4.13); IR (KBr): 3395,
2921, 2850, 1716, 1645, 1539, 1452, 1405, 1316, 1278, 1074, 903, 715; 1H-NMR (500 MHz, CD3OD): 5.17 (d, 7.6, H1), 7.37 (br s, H-3), 3.24 (br t, 7.2, H-5), 2.15 (dd, 16.6, 7.2, Ha -6), 2.90 (dd, 16.6, 7.2, Hb -6), 5.92 (br s, H-7), 2.80 (br t,
7.6, H-9), 5.07 (br d, 13.9, H-10), 5.01 (br d, 13.9, H-10), 4.73 (d, 7.8, H-1), 3.24 (t, 9.0, H-2), 3.38 (t, 9.0, H-3), overlapped ( H-4, 5), 3.84 (dd, 12.0, 1.8, H-6), 3.64 (dd, 12.0, 5.3, H-6), 8.04 (dd, 7.7, 1.2, H-2, 6), 7.48 (t, 7.7, H-3, 5),
7.60 (tt, 7.2, 1.2, H-4); 13C-NMR (125 MHz, CD3OD): 98.4 (C-1), 151.0 (C-3), 116.3 (C-4), 37.5 (C-5), 40.5 (C-6),
131.9 (C-7), 140.0 (C-8), 48.1 (C-9), 64.7 (C-10), 168.2 (C-11), 100.8 (C-1), 75.2 (C-2), 78.2 (C-3), 71.8 (C-4), 78.6
(C-5), 63.1 (C-6), 131.8 (C-1), 130.9 (C-2, 6), 129.9 (C-3, 5), 134.6 (C-4), 168.2 (C-7). Hedyotis corymbosa (Rubiaceae).32)
August 2009
52.
53.
54.
55.
56.
57.
773
Scyphiphorin A (10-O-Benzoylgeniposidic acid)

C23H26O11: 478.1475; white amorphous powder; [a ]D20 20.3 (c7.7, MeOH); UV (MeOH): 231 (4.38); IR (KBr):
3422, 2920, 1718, 1701, 1602, 1578, 1509, 1277, 1073, 757, 714, 686; 1H-NMR (500 MHz, CD3OD): 5.24 (d, 7.5, H-1),
7.55 (s, H-3), 3.213.25 (m, H-5), 2.152.19 (m, Ha -6), 2.892.92 (m, Hb -6), 5.94 (s, H-7), 2.822.86 (m, H-9),
5.10 (d, 13.9, H-10), 5.02 (d, 13.9, H-10), 4.78 (d, 8.0, H-1), 3.283.32 (m, H-2), 3.423.44 (m, H-3), 3.343.36
(m, H-4, 5), 3.873.89 (m, H-6), 3.663.70 (m, H-6), 8.05 (d, 7.5, H-2, 6), 7.50 (t, 7.5, H-3, 5), 7.61 (t, 7.5, H4); 13C-NMR (125 MHz, CD3OD): 98.4 (C-1), 153.4 (C-3), 112.6 (C-4), 36.5 (C-5), 40.0 (C-6), 131.5 (C-7), 139.5 (C8), 47.5 (C-9), 64.3 (C-10), 170.9 (C-11), 100.5 (C-1), 74.8 (C-2), 77.9 (C-3), 71.4 (C-4), 78.3 (C-5), 62.8 (C-6),
131.3 (C-1), 130.6 (C-2, 6), 129.6 (C-3, 5), 134.3 (C-4), 167.9 (C-7). Scyphiphora hydrophyllacea (Rubiaceae).33)
Scyphiphorin B
C26H38O12: 542.2263; white amorphous powder; [a ]D20 21.4 (c5.0, MeOH); UV (MeOH):
224 (4.74); IR (KBr): 3415, 2950, 1721, 1705, 1642, 1456, 1387; 1H-NMR (500 MHz,
CD3OD): 5.21 (d, 7.6, H-1), 7.54 (s, H-3), 3.213.23 (m, H-5), 2.142.19 (m, Ha -6), 2.86
2.91 (m, Hb -6), 5.86 (s, H-7), 2.762.80 (m, H-9), 4.92 (d, 13.8, H-10), 4.85 (d, 13.8, H-10),
4.74 (d, 7.9, H-1), 3.233.27 (m, H-2), 3.383.42 (m, H-3), 3.303.33 (m, H-4, 5),
3.863.90 (m, H-6), 3.643.69 (m, H-6), 6.84 (t, 7.2, H-3), 2.242.30 (m, H-4), 1.49
1.53 (m, H-5), 1.311.36 (m, H-5), 1.611.66 (m, H-6), 1.381.40 (m, H2-7), 3.58
3.62 (m, H2-8), 1.88 (s, H3-9), 0.95 (d, 6.5, Hf92/-10); 13C-NMR (125 MHz, CD3OD): 98.3 (C1), 153.4 (C-3), 112.7 (C-4), 36.5 (C-5), 40.0 (C-6), 131.0 (C-7), 139.9 (C-8), 47.6 (C-9), 63.9
(C-10), 170.9 (C-11), 100.6 (C-1), 74.9 (C-2), 78.0 (C-3), 71.5 (C-4), 78.5 (C-5), 62.9 (C6), 169.6 (C-1), 128.6 (C-2), 144.5 (C-3), 27.2 (C-4), 37.0 (C-5), 30.5 (C-6), 40.6 (C-7),
61.0 (C-8), 12.6 (C-9), 19.8 (C-10). Scyphiphora hydrophyllacea (Rubiaceae).33)
Marinoid D
C25H30O14: 554.1635; colorless oil; [a ]D20 3.1 (c1.5, MeOH); UV (MeOH): 278 (2.24), 218 (2.64); IR (KBr): 3422,
2925, 1704, 1629, 1514, 1462, 1425, 1336, 1225, 1111, 1078, 1041; 1H-NMR (500 MHz, DMSO-d6): 5.18 (d, 7.5, H-1),
7.41 (s, H-3), 3.15 (m, H-5), 2.13 (br dd, 6.0, 15.5, H-6), 2.78 (m, H-6), 5.91 (br s, H-7), 2.77 (m, H-9), 4.88 (d, 14.0, H10), 4.92 (d, 14.0, H-10), 4.56 (d, 8.0, H-1), 3.00 (dd, 8.0, 8.8, H-2), 3.17 (dd, 8.8, 9.0, H-3), 3.05 (dd, 9.0, 9.0, H-4),
3.13 (dd, 6.2, 9.0, H-5), 3.40 (dd, 11.2, 6.2, H-6), 3.62 (d, 11.2, H-6), 7.25 (s, H-2, 6), 3.82 (s, OMe); 13C-NMR
(125 MHz, DMSO-d6): 96.2 (C-1), 151.1 (C-3), 112.5 (C-4), 35.1 (C-5), 38.9 (C-6), 130.2 (C-7), 138.5 (C-8), 46.7 (C9), 63.0 (C-10), 169.1 (C-11), 99.2 (C-1), 73.7 (C-2), 77.0 (C-3), 70.4 (C-4), 77.7 (C-5), 61.5 (C-6), 119.7 (C-1),
107.3 (C-2,6), 148.0 (C-3,5), 141.1 (C-4), 166.8 (C-7), 56.5 (OMe). Avicennia marina (Avicenniaceae).34)
Marinoid E
C27H32O12: 548.1893; colorless oil; [a ]D20 10.8 (c0.6, MeOH); UV (MeOH): 246 (2.30); IR (KBr):
3412, 2924, 1721, 1642, 1606, 1512, 1451, 1421, 1252, 1158, 1077, 1039; 1H-NMR (500 MHz, DMSOd6): 5.00 (d, 7.5, H-1), 7.31 (s, H-3), 3.06 (m, H-5), 2.03 (br dd, 16.0, 7.0, H-6), 2.73 (br dd, 10.5, 9.0, H6), 5.83 (br s, H-7), 2.63 (m, H-9), 4.72 (br s, H2-10), 4.55 (d, 8.0, H-1), 3.00 (dd, 9.0, 8.0, H-2), 3.18
(dd, 9.0, 9.0, H-3), 3.02 (dd, 9.0, 9.0, H-4), 3.12 (dd, 9.0, 6.0, H-5), 3.40 (dd, 11.2, 6.0, H-6), 3.66
(br d, 11.2, H-6), 7.41 (d, 7.6, H-2, 6), 7.32 (dd, 7.6, 7.2, H-3, 5), 7.24 (dd, 7.2, 7.2, H-4), 6.57 (d,
15.9, H-7), 6.33 (dd, 15.9, 5.8, H-8), 4.56 (ddd, 6.0, 5.8, 4.8, H-9), 2.51 (dd, 15.4, 6.0, H-10), 2.64 (dd,
15.4, 4.8, H-10); 13C-NMR (125 MHz, DMSO-d6): 96.3 (C-1), 149.3 (C-3), 114.9 (C-4), 35.9 (C-5), 39.1
(C-6), 130.0 (C-7), 138.1 (C-8), 46.4 (C-9), 62.5 (C-10), 170.2 (C-11), 99.1 (C-1), 73.7 (C-2), 76.9 (C3), 70.4 (C-4), 77.7 (C-5), 61.5 (C-6), 137.0 (C-1), 126.7 (C-2, 6), 129.1 (C-3, 5), 127.9 (C-4),
129.1 (C-7), 133.1 (C-8), 68.5 (C-9), 43.0 (C-10), 170.9 (C-11). Avicennia marina (Avicenniaceae).34)
5-Dehydro-8-epi-adoxosidic acid
C16H22O10: 374.1213; isolated as pentaacetate; white amorphous powder; UV (MeOH): 280 (3.92), 234 (4.05); IR (KBr): 2646,
1747, 1705, 1655, 1636; 1H-NMR (400 MHz, CDCl3): 5.11 (d, 9.5, H-1), 7.52 (d, 1.0, H-3), 5.83 (br s, H-6), 2.19 (m, H-7), 2.83
(dd, 8.0, 2.0, H-7), 3.18 (ddd, 6.0, 6.0, 6.0, H-8), 2.86 (dd, 9.5, 6.0, H-9), 4.66 (dd, 14.0, 2.0, H2-10), 4.87 (d, 8.0, H-1), 5.01 (dd,
8.5, 8.0, H-2), 5.22 (dd, 9.0, 8.5, H-3), 5.08 (dd, 9.0, 8.5, H-4), 3.72 (m, H-5), 4.16 (dd, 12.5, 2.5, H-6), 4.24 (dd, 12.5, 4.5, H6), 1.98, 2.00, 2.02, 2.07, 2.08 (each s, 5Ac); 13C-NMR (100 MHz, CDCl3): 96.2 (C-1), 152.9 (C-3), 111.3 (C-4), 136.9 (C-5),
131.2 (C-6), 38.4 (C-7), 33.5 (C-8), 46.3 (C-9), 61.8 (C-10), 172.1 (C-11), 96.9 (C-1), 70.7 (C-2), 72.4 (C-3), 68.2 (C-4), 72.1
(C-5), 61.5 (C-6), 20.4, 20.52, 20.6, 20.8, 169.1, 169.32, 170.2, 170.6 (5Ac). Wendlandia tinctoria (Rubiaceae).35)
Tarenninoside A
C25H28O15: 568.1428; amorphous powder; [a ]D24 42.0 (c0.94, MeOH); UV (MeOH): 278 (3.93), 214 (4.50); IR
(KBr); 3424, 1702, 1623, 1551, 1517, 1463, 1405, 1337, 1229, 1169, 1037, 764; 1H-NMR (400 MHz, CD3OD): 5.62
(d, 3.8, H-1), 7.40 (s, H-3), 3.24 (m, H-5), 2.80 (dd, 18.0, 6.5, H-6), 2.23 (d, 18.0, H-6), 6.65 (br s, H-7), 3.16 (br s, H9), 4.69 (d, 7.8, H-1), 3.25 (m, H-2), 3.42 (m, H-3), 3.37 (m, H-4), 3.62 (m, H-5), 4.60 (d, 11.6, H-6), 4.39 (dd,
11.6, 6.4, H-6), 7.29 (s, H-2, 6), 3.86 (s, MeO-3, 5); 13C-NMR (100 MHz, CD3OD): 96.0 (C-1), 152.6 (C-3),
113.8 (C-4), 35.3 (C-5), 40.0 (C-6), 144.6 (C-7), 138.6 (C-8), 47.5 (C-9), not observed (C-10), 172.0 (C-11), 99.6 (C1), 74.6 (C-2), 77.6 (C-3), 71.9 (C-4), 75.7 (C-5), 65.2 (C-6), 121.2 (C-1), 108.2 (C-2, 6), 148.8 (C-3), 141.9
(C-4), 148.8 (C-5), 167.9 (C-7), 56.4 (MeO-3, 5). Tarenna attenuata (Rubiaceae).36)
58.
Tarenninoside B
(KBr); 3424, 1714, 1629, 1406, 1282, 1079, 962, 714; 1H-NMR (400 MHz, CD3OD): 5.58 (br s, H-1), 7.36 (s, H-3),
3.24 (m, H-5), 2.81 (m, H-6), 2.22 (m, H-6), 6.54 (br s, H-7), 3.15 (br s, H-9), 4.68 (d, 7.4, H-1), 3.25 (m, H-2), 3.42
(m, H-3), 3.39 (m, H-4), 3.60 (m, H-5), 4.60 (d, 11.5, H-6), 4.40 (dd, 11.5, 6.1, H-6), 7.99 (d, 7.5, H-2, 6), 7.46
(dd, 7.5, 7.0, H-3, 5), 7.58 (t, H-4); 13C-NMR (100 MHz, CD3OD): 96.4 (C-1), 152.2 (C-3), 114.8 (C-4), 35.4 (C5), 40.1 (C-6), 141.5 (C-7), 138.6 (C-8), 47.8 (C-9), not observed (C-10, 11), 99.8 (C-1), 74.6 (C-2), 77.7 (C-3),
72.0 (C-4), 75.6 (C-5), 65.3 (C-6), 131.3 (C-1), 130.6 (C-2, 6), 129.6 (C-3, 5), 134.3 (C-4), 168.0 (C-7).
Tarenna attenuata (Rubiaceae).36)
774
59.
Vol. 57, No. 8

Tarenninoside C
C24H26O14: 538.1322; amorphous powder; [a ]D20 37.0 (c1.32, MeOHC5H5N, 1 : 1); UV (MeOH): 362 (2.31),
292 (3.59), 251 (3.96), 220 (4.29); IR (KBr): 3420, 1705, 1631, 1595, 1517, 1405, 1285, 1181, 1078, 763; 1H-NMR
(500 MHz, C5D5N): 5.72 (br s, H-1), 7.42 (s, H-3), 3.26 (br s, H-5), 2.81 (m, H-6), 2.30 (m, H-6), 6.64 (br s, H-7),
3.20 (br s, H-9), 4.71 (d, 7.6, H-1), 3.30 (m, H-2), 3.46 (m, H-3), 3.43 (m, H-4), 3.62 (m, H-5), 4.60 (m, H-6),
4.37 (m, H-6), 7.51 (s, H-2), 6.83 (d, 7.2, H-5), 7.54 (d, 7.2, H-6), 3.84 (s, MeO-3); 13C-NMR (125 MHz,
C5D5N): 96.2 (C-1), 152.6 (C-3), 111.1 (C-4), 35.5 (C-5), 40.0 (C-6), 142.0 (C-7), not observed (C-8, 10, 11), 47.9
(C-9), 100.0 (C-1), 74.6 (C-2), 77.8 (C-3), 71.9 (C-4), 75.8 (C-5), 65.1 (C-6), 122.4 (C-1), 113.7 (C-2), 148.7
(C-3), 153.0 (C-4), 116.1 (C-5), 125.5 (C-6), 167.9 (C-7), 56.5 (MeO-3). Tarenna attenuata (Rubiaceae).36)
60.
Tarenninoside D
C26H28O14: 564.1478; amorphous powder; [a ]D20 23.5 (c1.69, MeOHC5H5N, 1 : 1); UV (MeOH): 325 (4.02),
263 (3.67); IR (KBr); 3424, 1698, 1631, 1596, 1516, 1441, 1402, 1356, 1282, 1162, 1082, 754; 1H-NMR (500 MHz,
C5D5N): 5.78 (br s, H-1), 7.45 (s, H-3), 3.28 (br s, H-5), 2.81 (br s, H-6), 2.38 (br s, H-6), 6.65 (br s, H-7), 3.19 (br s,
H-9), 4.74 (d, 7.2, H-1), 3.30 (m, H-2), 3.52 (m, H-3), 3.48 (m, H-4), 3.59 (m, H-5), 4.49 (m, H-6), 4.38 (m, H6), 7.17 (s, H-2), 6.81 (d, 7.7, H-5), 7.12 (d, 7.7, H-6), 7.59 (d, 14.9, H-7), 6.34 (d, 14.9, H-8), 3.82 (s, MeO-3);
13
C-NMR (125 MHz, C5D5N): 96.2 (C-1), 152.5 (C-3), 35.5 (C-5), 40.0 (C-6), 145.6 (C-7), 47.9 (C-9), not observed
(C-4, 8, 10, 11), 100.1 (C-1), 74.6 (C-2), 77.7 (C-3), 71.6 (C-4), 75.6 (C-5), 64.6 (C-6), 128.0 (C-1), 111.8 (C2), 149.4 (C-3), 150.7 (C-4), 116.6 (C-5), 124.2 (C-6), 146.9 (C-7), 115.4 (C-8), 167.9 (C-9), 56.5 (MeO-3).
61.
Tarenninoside E
(KBr): 3415, 1702, 1634, 1551, 1517, 1450, 1403, 1313, 1204, 1080, 1038, 769; 1H-NMR (400 MHz, CD3OD): 5.66
(br s, H-1), 7.43 (s, H-3), 3.25 (m, H-5, 2), 2.81 (br s, H-6), 2.35 (br s, H-6), 6.65 (br s, H-7), 3.18 (br s, H-9), 4.68 (d,
6.8, H-1), 3.40 (m, H-3), 3.38 (m, H-4), 3.56 (m, H-5), 4.48 (m, H-6), 4.35 (m, H-6), 7.57 (d, 7.3, H-2, 6), 7.38
(br s, H-3, 4, 5), 7.67 (d, 16.0, H-7), 6.54 (d, 16.0, H-8); 13C-NMR (100 MHz, CD3OD): 96.1 (C-1), 152.6 (C-3),
113.9 (C-4), 35.3 (C-5), 40.0 (C-6), 144.0 (C-7), 47.7 (C-9), not observed (C-8, 10, 11), 99.9 (C-1), 74.5 (C-2),
77.6 (C-3), 71.6 (C-4), 75.5 (C-5), 64.8 (C-6), 135.6 (C-1), 129.3 (C-2,6), 130.0 (C-3,5), 131.5 (C-4), 146.5
(C-7), 118.6 (C-8), 168.5 (C-9). Tarenna attenuata (Rubiaceae).36)
62.
Tarenninoside F
C26H28O14: 564.1478; amorphous powder; [a ]D20 7.3 (c0.68, MeOHC5H5N, 1 : 1); UV (MeOH): 325 (3.83), 216
(3.96); IR (KBr); 3431, 1605, 1517, 1364, 1282, 1159, 1087, 1033, 755; 1H-NMR (400 MHz, CD3OD): 5.66 (br s, H1), 7.42 (s, H-3), 3.28 (br s, H-5), 2.86 (m, H-6), 2.37 (d, 16.4, H-6), 6.60 (br s, H-7), 3.20 (br s, H-9), 4.69 (d, 7.8, H1), 3.52 (m, H-2), 3.32 (m, H-3), 4.85 (m, H-4), 3.63 (m, H-5), 3.62 (m, H-6), 3.51 (m, H-6), 7.18 (d, 1.5, H2), 6.81 (d, 8.2, H-5), 7.08 (d, 8.2, H-6), 7.65 (d, 15.8, H-7), 6.39 (d, 15.8, H-8), 3.88 (s, MeO-3); 13C-NMR
(100 MHz, CD3OD): 96.8 (C-1), 152.5 (C-3), 35.2 (C-5), 40.1 (C-6), 142.2 (C-7), 48.0 (C-9), not observed (C-4, 8,
10, 11), 100.3 (C-1), 74.7 (C-2), 76.3 (C-3), 72.3 (C-4), 75.6 (C-5), 62.3 (C-6), 127.7 (C-1), 111.8 (C-2),
149.4 (C-3), 150.8 (C-4), 116.5 (C-5), 124.2 (C-6), 147.6 (C-7), 115.1 (C-8), 168.6 (C-9), 56.5 (MeO-3).
63.
Tarenninoside G
C24H26O14: 538.1322; amorphous powder; [a ]D24 26.4 (c0.42, MeOH); UV (MeOH): 391 (2.49), 292 (3.69), 260
(3.98), 217 (4.36); IR (KBr); 3430, 1698, 1633, 1602, 1553, 1519, 1403, 1285, 1107, 1081, 762; 1H-NMR (400 MHz,
CD3OD): 5.67 (br s, H-1), 7.42 (s, H-3), 3.28 (br s, H-5), 2.86 (d, 17.4, H-6), 2.36 (d, 17.4, H-6), 6.59 (br s, H-7), 3.18
(br s, H-9), 4.76 (d, 7.7, H-1), 3.49 (m, H-2), 5.15 (t, 9.4, H-3), 3.63 (m, H-4), 3.41 (m, H-5), 3.85 (br s, H-6),
3.71 (m, H-6), 7.60 (s, H-2), 6.84 (d, 8.0, H-5), 7.61 (d, 8.0, H-6), 3.89 (s, MeO-3); 13C-NMR (100 MHz,
CD3OD): 96.7 (C-1), 152.6 (C-3), 35.3 (C-5), 40.1 (C-6), 142.0 (C-7), 48.0 (C-9), not observed (C-4, 8, 10, 11),
100.2 (C-1), 73.1 (C-2), 79.0 (C-3), 69.6 (C-4), 78.1 (C-5), 62.3 (C-6), 122.8 (C-1), 113.9 (C-2), 148.6 (C-3),
152.8 (C-4), 115.8 (C-5), 125.3 (C-6), 168.1 (C-7), 54.6 (MeO-3). Tarenna attenuata (Rubiaceae).36)
64.
Marinoid A
C25H30O11: 506.1788; colorless oil; [a ]D20 72.9 (c0.7, MeOH); UV (MeOH): 282 (2.98), 221 (2.79); IR (KBr):
3394, 2930, 1711, 1649, 1550, 1420, 1182, 1074, 1027; 1H-NMR (500 MHz, DMSO-d6): 5.18 (br s, H-1), 7.09 (s, H3), 2.87 (m, H-5), 1.29 (m, H-6), 2.09 (m, H-6), 1.52 (m, H2-7), 1.90 (m, H-9), 1.18 (s, H3-10), 4.81 (d, 8.6, H-1),
4.66 (dd, 9.1, 8.6, H-2), 3.49 (dd, 9.1, 9.0, H-3), 3.18 (dd, 9.0, 9.0, H-4), 3.27 (br dd, 9.0, 5.5, H-5), 3.47 (dd, 11.0,
5.5, H-6), 3.72 (br d, 11.0, H-6), 7.69 (m, H-2, 6), 7.42 (m, H-3, 4, 5), 7.59 (d, 16.0, H-7), 6.53 (d, 16.0, H-8);
13
C-NMR (125 MHz, DMSO-d6): 94.2 (C-1), 147.5 (C-3), 115.2 (C-4), 31.6 (C-5), 30.0 (C-6), 39.9 (C-7), 78.7 (C8), 51.2 (C-9), 27.1 (C-10), 171.5 (C-11), 96.5 (C-1), 74.0 (C-2), 74.4 (C-3), 70.6 (C-4), 76.5 (C-5), 61.3 (C-6),
134.6 (C-1), 128.8 (C-2, 6), 129.4 (C-3, 5), 130.7 (C-4), 144.7 (C-7), 118.7 (C-8), 165.6 (C-9). Avicennia marina (Avicenniaceae).34)
65.
Marinoid B
C26H32O12: 536.1893; colorless oil; [a ]D20 53.5 (c1.9, MeOH); UV (MeOH): 312 (2.69), 229 (2.61);
IR (KBr): 3416, 2926, 1709, 1641, 1604, 1513, 1422, 1254, 1173, 1071, 1024; 1H-NMR (500 MHz,
DMSO-d6): 5.19 (br s, H-1), 7.11 (s, H-3), 2.86 (m, H-5), 1.29 (m, H-6), 2.09 (m, H-6), 1.52 (m, H2-7),
1.91 (m, H-9), 1.18 (s, H3-10), 4.79 (d, 8.1, H-1), 4.65 (dd, 9.1, 8.1, H-2), 3.46 (dd, 9.1, 9.0, H-3), 3.19
(dd, 9.0, 9.0, H-4), 3.28 (br dd, 9.0, 6.0, H-5), 3.49 (dd, 11.0, 6.0, H-6), 3.72 ( br d, 11.1, H-6), 7.64 (d,
8.5, H-2, 6), 6.97 (d, 8.5, H-3, 5), 7.54 (d, 15.9, H-7), 6.37 (d, 15.9, H-8), 3.80 (s, MeO-4); 13CNMR (125 MHz, DMSO-d6): 94.1 (C-1), 147.8 (C-3), 116.4 (C-4), 31.5 (C-5), 29.9 (C-6), 40.5 (C-7),
78.7 (C-8), 51.2 (C-9), 27.7 (C-10), 171.9 (C-11), 96.5 (C-1), 73.8 (C-2), 74.5 (C-3), 70.6 (C-4), 77.9
(C-5), 61.3 (C-6), 127.3 (C-1), 130.6 (C-2, 6), 114.8 (C-3, 5), 161.4 (C-4), 144.5 (C-7), 116.0 (C8), 165.9 (C-9), 55.7 (MeO-4). Avicennia marina (Avicenniaceae).34)
August 2009
66.
67.
68.
69.
70.
71.
775
Marinoid C
C25H30O12: 522.1737; colorless oil; [a ]D20 75.0 (c0.2, MeOH); UV (MeOH): 313 (2.22), 230 (2.14); IR (KBr):
3418, 2925, 1701, 1648, 1605, 1514, 1419, 1260, 1172, 1074, 1025; 1H-NMR (500 MHz, DMSO-d6): 5.17 (br s,
H-1), 7.07 (s, H-3), 2.88 (m, H-5), 1.30 (m, H-6), 2.09 (m, H-6), 1.52 (m, H2-7), 1.87 (m, H-9), 1.18 (s, H3-10),
4.80 (d, 8.0, H-1), 4.65 (dd, 9.0, 8.0, H-2), 3.47 (dd, 9.0, 9.0, H-3), 3.18 (dd, 9.0, 9.0, H-4), 3.26 (br dd, 6.0, 9.0,
H-5), 3.47 (dd, 11.0, 6.0, H-6), 3.72 (br d, 11.0, H-6), 7.53 (d, 8.5, H-2, 6), 6.80 (d, 8.5, H-3, 5), 7.51 (d,
16.0, H-7), 6.31 (d, 16.0, H-8); 13C-NMR (125 MHz, DMSO-d6): 94.1 (C-1), 147.6 (C-3), 116.2 (C-4), 31.4 (C5), 29.8 (C-6), 40.6 (C-7), 78.6 (C-8), 51.1 (C-9), 27.3 (C-10), 171.6 (C-11), 96.4 (C-1), 73.6 (C-2), 74.5 (C-3),
70.7 (C-4), 77.8 (C-5), 61.3 (C-6), 125.7 (C-1), 130.7 (C-2, 6), 116.2 (C-3, 5), 160.4 (C-4), 144.9 (C-7),
116.2 (C-8), 166.0 (C-9). Avicennia marina (Avicenniaceae).34)
2-O[(2E,4E)-5-Phenylpenta-2,4-dienoyl] mussaenosidic acid
C27H32O11: 532.1944; colorless amorphous powder; [a ]D22 122.1 (c0.21, MeOH); UV
(MeOH): 311 (4.42), 232 (4.18); IR (KBr): 3396, 2962, 1701, 1625, 1073; 1H-NMR (500 MHz,
CD3OD): 5.49 (d, 2.4, H-1), 7.29 (s, H-3), 2.973.02 (m, H-5), 2.182.22 (m, Ha -6), 1.45
1.51 (m, Hb -6), 1.651.73 (m, Ha -7), 1.601.64 (m, Hb -7), 2.25 (dd, 9.5, 2.2, H-9), 1.28 (s,
H3-10), 4.87 (overlapped, H-1), 4.79 (dd, 9.3, 8.3, H-2), 3.62 (dd, 8.9, 8.5, H-3), 3.363.38
(m, H-4), 3.383.40 (m, H-5), 3.93 (d, 11.5, H-6), 3.71 (dd, 11.5, 5.1, H-6), 7.56 (d, 7.4, H2, 6), 7.36 (t, 7.4, H-3, 5), 7.31 (t, 7.4, H-4), 7.007.01 (m, H-7), 6.997.00 (m, H-8),
7.427.47 (m, H-9), 5.99 (d,15.3, H-10); 13C-NMR (125 MHz, CD3OD): 95.0 (C-1), 151.1
(C-3), 114.4 (C-4), 31.4 (C-5), 30.3 (C-6), 41.5 (C-7), 79.8 (C-8), 52.6 (C-9), 24.4 (C-10), not
observed (C-11), 97.6 (C-1), 74.8 (C-2), 76.0 (C-3), 71.8 (C-4), 78.6 (C-5), 62.8 (C-6),
137.7 (C-1), 128.4 (C-2, 6), 129.8 (C-3, 5), 130.0 (C-4), 142.6 (C-7), 127.6 (C-8), 146.8
(C-9), 121.6 (C-10), 167.8 (C-11). Avicennia marina (Verbenaceae).37)
2-O-(4-Methoxycinnamoyl) mussaenosidic acid
(4.27), 221 sh (4.34), 207 (4.47); IR (KBr): 3403, 2963, 1700, 1635, 1603, 1513, 1253, 1173, 1072, 1028; 1HNMR (500 MHz, CD3OD): 5.49 (d, 2.5, H-1), 7.28 (s, H-3), 2.993.02 (m, H-5), 2.222.24 (m, Ha -6),
1.431.49 (m, Hb -6), 1.681.72 (m, Ha -7), 1.621.66 (m, Hb -7), 2.25 (dd, 9.5, 2.5, H-9), 1.28 (s, H3-10),
4.90 (d, 8.2, H-1), 4.81 (dd, 9.4, 8.2, H-2), 3.623.65 (m, H-3), 3.373.39 (m, H-4), 3.393.40 (m, H5), 3.94 (d, 12.0, H-6), 3.71 (dd, 12.0, 5.5, H-6), 7.54 (d, 8.7, H-2, 6), 6.96 (d, 8.7, H-3, 5), 7.62 (d, 15.9,
H-7), 6.32 (d, 15.9, H-8), 3.84 (s, MeO-4); 13C-NMR (125 MHz, CD3OD): 95.1 (C-1), 151.2 (C-3), 114.2
(C-4), 31.5 (C-5), 30.3 (C-6), 41.4 (C-7), 79.9 (C-8), 52.6 (C-9), 24.4 (C-10), 170.2 (C-11), 97.8 (C-1), 74.8
(C-2), 76.0 (C-3), 71.7 (C-4), 78.6 (C-5), 62.8 (C-6), 128.6 (C-1), 131.1 (C-2, 6), 115.4 (C-3, 5),
163.1 (C-4), 146.4 (C-7), 116.0 (C-8), 168.0 (C-9), 55.9 (OMe). Avicennia marina (Avicenniaceae).37)
8-Deoxyshanzhiside
C16H24O10: 376.1369; crystals; mp 213214 C; [a ]D25 155.7 (c0.18, H2O); UV (MeOH): 237 (6.33); IR (KBr): 3613,
3467, 3382, 2943, 2884, 1676, 1641; 1H-NMR (400 MHz, D2O): 5.44 (d, 2.0, H-1), 7.34 (s, H-3), 2.70 (d, 9.0, H-5), 4.11
(t, 2.0, H-6), 1.38 (ddd, 13.0, 10.0, 4.0, H-7), 1.65 (dd, 13.0, 8.0, H-7), 2.43 (m, H-8), 2.56 (dt, 9.2, 2.0, H-9), 0.87 (d, 7.0,
H3-10), 4.63 (d, 8.0, H-1), 3.10 (t, 9.0, H-2), 3.33 (t, 9.0, H-3), 3.23 (t, 9.0, H-4), 3.33 (t, 9.0, H-5), 3.62 (dd, 12.0, 6.0,
H-6), 3.77 (d, 12.0, H-6); 13C-NMR (100 MHz, D2O): 96.0 (C-1), 153.3 (C-3), 110.3 (C-4), 412.1 (C-5), 77.1 (C-6), 40.8
(C-7), 32.5 (C-8), 40.5 (C-9), 15.7 (C-10), 171.1 (C-11), 98.6 (C-1), 72.9 (C-2), 75.9 (C-3), 69.9 (C-4), 76.5 (C-5),
61.0 (C-6). Lamiophlomis rotata (Labiatae).38)
Lamalbidic acid
C16H24O12: 408.1267; amorphous powder; [a ]D33 122.0 (c0.1, MeOH); UV (MeOH): 232 (3.94); IR (KBr): 3420, 2921,
1684, 1646; 1H-NMR (400 MHz, D2O): 5.66 (d, 0.8, H-1), 7.47 (s, H-3), 2.94 (dd, 11.0, 3.4, H-5), 4.08 (dd, 4.4, 3.4, H-6),
3.70 (d, 4.4, H-7), 2.84 (s, H-9), 1.23 (s, H3-10), 4.78 (d, 8.1, H-1), 3.27 (dd, 9.3, 8.1, H-2), 3.50 (t, 9.3, H-3), 3.40 (t, 9.5,
H-4), 3.52 (overlapped, H-5), 3.93 (dd, 12.4, 2.1, H-6), 3.72 (dd, 12.4, 6.1, H-6); 13C-NMR (100 MHz, D2O): 94.5 (C-1),
152.4 (C-3), 111.4 (C-4), 36.1 (C-5), 76.6 (C-6), 78.8 (C-7), 78.5 (C-8), 47.9 (C-9), 21.3 (C-10), 171.7 (C-11), 98.8 (C-1),
73.3 (C-2), 76.7 (C-3), 70.2 (C-4), 77.1 (C-5), 61.5 (C-6). Eremostachys moluccelloides (Lamiaceae).39)
6-O-[(E)-Sinapoyl] gardoside
C27H32O14: 580.1791; pale yellow powder; [a ]D22 5.8 (c0.25, MeOH); UV (MeOH): 326 (4.64), 234 (4.14); IR
(KBr): 3438, 2923, 1635, 1558, 1516, 1456, 1404, 1258, 1157, 577; 1H-NMR (500 MHz, CD3OD): 5.11 (d, 7.6, H1), 7.14 (br s, H-3), 3.04 (d, 8.4, H-5), 1.831.84 (m, H-6), 4.274.30 (m, H-7), 2.832.84 (m, H-9), 5.15 (br d,
7.7, H2-10), 4.57 (d, 7.8, H-1), 3.143.18 (m, H-2), 3.313.35 (m, H-3), 3.253.28 (m H-4), 3.463.49 (m,
H-5), 4.41 (dd, 12.3, 1.9, H-6), 4.38 (dd, 12.3, 5.1, H-6), 6.81 (br d, H-2, 6), 7.53 (d, 15.8, H-7), 6.37 (d, 15.8,
H-8), 3.77 (s, MeO-3, 5); 13C-NMR (125 MHz, CD3OD): 97.0 (C-1), 153.9 (C-3), 112.4 (C-4), 31.6 (C-5), 41.0
(C-6), 73.9 (C-7), 152.2 (C-8), 44.9 (C-9), 112.7 (C-10), 169.5 (C-11), 101.1 (C-1), 74.9 (C-2), 78.5 (C-3), 71.5
(C-4), 75.9 (C-5), 64.4 (C-6), 125.3 (C-1), 107.0 (C-2, 6), 149.7 (C-3, 5), 140.8 (C-4), 146.2 (C-7), 115.5
(C-8), 167.6 (C-9), 56.6 (MeO-3, 5). Gardenia jasminoides (Rubiaceae).40)
72.
6-O-E-p-Coumaroylgardoside
C25H28O12: 520.1580; yellowish oil; [a ]D20 4.29 (c0.12, MeOH); UV (MeOH): 300.5 sh (4.42), 312
(4.89); IR (film); 3352, 2914, 1644, 1607; 1H-NMR (400 MHz, CD3OD): 5.25 (d, 4.2, H-1), 7.13 (s, H-3),
3.19 (d, 8.0, H-5), 1.902.10 (m, H2-6), 4.39 (m, H-7), 2.9 (m, H-9), 5.19 (br d, 7.5, H2-10), 4.65 (d, 8.0, H1), 3.25 (dd, 9.5, 8.0, H-2), 3.40 (t, 9.5, H-3), 3.33 (t, 9.5, H-4), 3.50 (m, H-5), 4.47 (dd, 12.0, 2.2, H-6),
4.38 (dd, 12.0, 6.2, H-6), 7.57 (d, 8.5, H-2, 6), 6.80 (d, 8.5, H-3, 5), 7.63 (d, 16.0, H-7), 6.36 (d, 15.7, H8); 13C-NMR (100 MHz, CD3OD): 96.5 (C-1), 147.2 (C-3), 113.5 (C-4), 31.0 (C-5), 40.9 (C-6), 72.8 (C-7),
150.9 (C-8), 45.9 (C-9) 112.0 (C-10), 171.2 (C-11), 99.5 (C-1), 73.5 (C-2), 77.0 (C-3), 70.9 (C-4), 74.8
(C-5), 63.8 (C-6), 127.9 (C-1), 130.2 (C-2, 6), 115.7 (C-3, 5), 160.1 (C-4), 147.0 (C-7), 114.9 (C-8),
168.7 (C-9). Scutellaria albida ssp. albida (Lamiaceae).28)
776
73.
Vol. 57, No. 8

Genameside A
C17H26O12: 422.1423; colourless syrup; [a ]D26 91.9 (c2.4, MeOH); 1H-NMR (500 MHz, CD3OD): 5.68 (d, 8.0, H-1),
7.45 (d, 1.0, H-3), 3.29 (m, H-5), 2.80 (ddd, 14.5, 10.0, 7.0, Ha-6), 1.37 (ddd, 14.5, 8.0, 4.0, Hb-6), 4.03 (dd, 7.0, 4.0, H-7),
2.19 (dd, 8.0, 8.0, H-9), 3.98 (d,12.0, Ha-10), 3.83 (d, 12.0, Hb-10), 3.71 (s, OMe), 4.73 (d, 8.0, H-1), 3.23 (dd, 9.0, 8.0, H2), 3.39 (deformed, H-3), 3.30 (H-4, 5), 3.86 (d, 11.5, Ha-6), 3.67 (deformed, Hb-6); 13C-NMR (125 MHz, CD3OD):
95.4 (C-1), 152.5 (C-3), 112.8 (C-4), 31.9 (C-5), 41.5 (C-6), 79.0 (C-7), 84.7 (C-8), 49.4 (C-9), 64.4 (C-10), 169.4 (C-11),
51.7 (OMe), 100.2 (C-1), 74.8 (C-2), 77.9 (C-3), 71.7 (C-4), 78.3 (C-5), 62.9 (C-6). Genipa americana (Rubiaceae).41)
74.
Genameside B
C17H26O12: 422.1423; colorless syrup: [a ]D26 63.8 (c1.9, MeOH); 1H-NMR (500 MHz, CD3OD): 5.53 (d, 3.5, H-1), 7.41
(s, H-3), 3.15 (ddd, 8.0, 8.0, 8.0, H-5), 2.18 (ddd, 13.5, 7.5, 3.0, Ha-6), 1.82 (ddd, 13.5, 8.0, 5.0, Hb-6), 3.94 (dd, 5.0, 3.0, H7), 2.44 (dd, 8.0, 3.5, H-9), 3.78 (d, 11.5, Ha-10), 3.72 (d, 11.5, Hb-10), 3.70 (s, OMe), 4.67 (d, 8.0, H-1), 3.20 (dd, 9.0, 8.0,
H-2), 3.37 (deformed, H-3), 3.31 (ca. H-4, 5), 3.86 (d, 11.5, Ha-6), 3.68 (ca. Hb-6); 13C-NMR (125 MHz, CD3OD): 96.3
(C-1), 152.6 (C-3), 113.7 (C-4), 31.4 (C-5), 40.5 (C-6), 79.3 (C-7), 84.5 (C-8), 45.4 (C-9), 66.4 (C-10), 169.4 (C-11), 51.7
(OMe), 100.6 (C-1), 74.7 (C-2), 78.0 (C-3), 71.4 (C-4), 78.9 (C-5), 62.6 (C-6). Genipa americana (Rubiaceae).41)
75.
Genameside C
C23H34O15: 550.1897; white powder; [a ]D26 0.4 (c3.3, MeOH); 1H-NMR (500 MHz, CD3OD): 5.13 (d, 8.0, H-1), 7.51
(d, 2.0, H-3), 3.19 (ddd, 8.0, 8.0, 8.0, H-5), 2.82 (dd, 16.5, 8.0, Ha-6), 2.08 (dddd, 16.5, 8.0, 2.0, 2.0, Hb-6), 5.80 (br s, H7), 2.72 (dd, 8.0, 8.0, H-9), 4.31 (br d, 14.0, Ha-10), 4.18 (dd,14.0, 2.0, Hb-10), 3.71 (s, OMe), 4.74 (d, 8.0, H-1), 3.30
(ca. H-2), 3.55 (dd, 9.0, 9.0, H-3), 3.58 (dd, 9.0, 9.0, H-4), 3.43 (ddd, 9.0, 4.0, 2.5, H-5), 3.89 (dd, 11.5, 2.5, Ha-6),
3.83 (dd, 11.5, 4.0, Hb-6), 4.41 (d, 8.0, H-1), 3.23 (dd, 9.0, 8.0, H-2), 3.38 (dd, 9.0, 9.0, H-3), 3.30 (ca. H-4), 3.35 (ca.
H-5), 3.88 (dd, 11.5, 2.5, Ha-6), 3.66 (dd, 11.5, 5.5, Hb-6); 13C-NMR (125 MHz, CD3OD): 98.4 (C-1), 153.3 (C-3),
112.6 (C-4), 36.6 (C-5), 39.7 (C-6), 128.4 (C-7), 144.8 (C-8), 47.0 (C-9), 61.4 (C-10), 169.5 (C-11), 51.7 (OMe), 100.3
(C-1), 74.9 (C-2), 76.9 (C-3), 80.6 (C-4), 76.2 (C-5), 61.8 (C-6),104.6 (C-1), 74.6 (C-2), 77.9 (C-3), 74.1 (C-4),
78.1 (C-5), 62.5 (C-6). Genipa americana (Rubiaceae).41)
76.
Genameside D
C23H34O15: 550.1897; colorless syrup; [a ]D26 3.3 (c6.0, MeOH); 1H-NMR (500 MHz, CD3OD): 5.25 (d, 6.5, H-1), 7.50
(d,1.0, H-3), 3.21 (ca., H-5), 2.83 (dd, 16.5, 8.5, Ha-6), 2.11 (br ddq, 16.5, 5.5, Hb-6), 6.88 (br s, H-7), 2.95 (dd, 7.5, 7.5, H9), 4.61 (d, 13.0, Ha-10), 4.27 (d, 13.0, Hb-10), 3.71 (s, OMe), 4.72 (d, 8.0, H-1), 3.26 (ca. H-2), 3.39 (ca. H-3), 3.31 (ca.
H-4), 3.30 (ca. H-5), 3.87 (dd, 11.5, 1.0, Ha-6), 3.66 (ca. Hb-6), 4.35 (d, 8.0, H-1), 3.26 (ca. H-2), 3.39 (ca. H-3), 3.31
(ca. H-4), 3.30 (ca. H-5), 3.87 (dd, 11.5, 1.0, Ha-6), 3.68 (ca. Hb-6); 13C-NMR (125 MHz, CD3OD): 97.9 (C-1), 153.4
(C-3), 112.8 (C-4), 36.0 (C-5), 39.8 (C-6), 130.6 (C-7), 141.5 (C-8), 47.1 (C-9), 69.1 (C-10), 169.7 (C-11), 51.9 (OMe),
100.3 (C-1), 74.9 (C-2), 77.9 (C-3), 71.7 (C-4), 78.1 (C-5), 62.8 (C-6), 104.6 (C-1), 75.3 (C-2), 78.0 (C-3), 71.4 (C4), 78.4 (C-5), 62.9 (C-6). Genipa americana (Rubiaceae).41)
77.
78.
79.
80.
6-O-Sinapoylgeniposide
C28H34O14: 594.1948; pale yellow powder; [a ]D20 6.7 (c0.05, MeOH); UV (MeOH): 325, 235; 1H-NMR (500
MHz, CD3OD): 4.97 (d, 8.1, H-1), 7.46 (s, H-3), 3.11 (m, H-5), 2.73 (m, H-6), 1.95 (m, H-6), 5.76 (br s, H-7),
2.68 (m, H-9), 4.24 (d, 14.0, H-10), 4.17 (d, 14.0, H-10), 4.70 (d, 7.9, H-1), 3.28 (m, H-2), 3.39 (m, H-3), 3.42
(m, H-4), 3.53 (m, H-5), 4.46 (m, H-6), 4.39 (m, H-6), 6.88 (s, H-2, 6), 7.58 (d, 15.8, H-7), 6.36 (d, 15.8, H8), 3.64 (s, MeO-11), 3.87 (MeO-3, 5); 13C-NMR (125 MHz, CD3OD): 98.8 (C-1), 153.2 (C-3), 112.5 (C-4),
36.9 (C-5), 39.9 (C-6), 128.8 (C-7), 145.0 (C-8), 46.6 (C-9), 61.6 (C-10), 169.4 (C-11), 100.6 (C-1), 74.9 (C-2),
77.8 (C-3), 71.9 (C-4), 75.8 (C-5), 64.4 (C-6), 126.6 (C-1), 107.1 (C-2, 6), 149.5 (C-3, 5), 139.5 (C-4),
147.3 (C-7), 115.8 (C-8), 168.9 (C-9), 51.7 (MeO-11), 56.9 (MeO-3, 5). Gardenia jasminoides (Rubiaceae).42)
Genipin-1-O-a -L-rhamnopyranosyl(16)-b -D-glucopyranoside
C23H34O14: 534.1948; colorless gum; [a ]D20 25.7 (c0.04, MeOH); UV (MeOH): 234 (3.45); IR (KBr); 3358, 2951,
1704, 1629, 1589, 1408, 1282, 1248, 1157, 1074, 985, 942, 896, 842; 1H-NMR (500 MHz, D2O): 5.22 (d, 7.6, H-1),
7.60 (s, H-3), 3.25 (q, 7.6, H-5), 2.16 (dd, 16.4, 7.6, H-6), 2.84 (dd, 16.4, 7.6, H-6), 5.91 (br s, H-7), 2.87 (t, 7.6, H-9),
4.28 (d, 14.0, H-10), 4.32 (d, 14.0, H-10), 3.77 (s, OMe), 4.84 (d, 8.4, H-1), 3.38 (dd, 9.2, 8.4, H-2), 3.54 (dd, 9.2, 9.2,
H-3), 3.44 (dd, 9.2, 9.2, H-4), 3.60 (dd, 9.2, 5.6, H-5), 3.70 (dd, 10.8, 5.6, H-6), 4.01 (br d, 10.8, H-6), 4.83 (br s, H1), 3.95 (br s, H-2), 3.73 (m, H-3), 3.42 (br d, 8.8, H-4), 3.67 (dq, 8.8, 6.0, H-5), 1.30 (d, 6.0, H3-6); 13C-NMR
(125 MHz, D2O): 100.6 (C-1), 155.8 (C-3), 114.8 (C-4), 37.6 (C-5), 41.2 (C-6), 132.7 (C-7), 144.5 (C-8), 48.7 (C-9),
63.0 (C-10), 173.5 (C-11), 55.0 (OMe), 102.1 (C-1), 75.9 (C-2), 78.8 (C-3), 72.8 (C-4), 78.2 (C-5), 70.0 (C-6),
103.8 (C-1), 73.2 (C-2), 73.4 (C-3), 75.2 (C-4), 71.9 (C-5), 19.8 (C-6). Adina polycephala (Rubiaceae).43)
6-O-Cyclopropanoyltheviridoside
C21H28O12: 472.1580; pale yellow amorphous powder; [a ]D25 27.3 (c1.0, MeOH); UV (MeOH): 324 (3.01),
282 (3.13), 231 (3.79), 200 (4.04); 1H-NMR (500 MHz, CD3OD): 5.36 (d, 5.9, H-1), 7.49 (s, H-3), 2.82 (dd, 17.6,
9.8, H2-6), 5.72 (d, 1.5, H-7), 3.03 (d, 4.9, H-9), 4.18 (dd, 25.4, 16.7, H2-10), 3.73 (s, MeO),4.64 (d, 7.8, H-1),
3.22 (m, H-2), 3.36 (t, 9.0, H-3), 3.31 (m, H-4), 3.47 (m, H-5), 4.36 (dd, 12.0, 2.2, H-6), 4.22 (dd, 11.7, 5.9,
H-6), 1.65 (m, H-2), 0.91 (m, H4-3, 4); 13C-NMR (125 MHz, CD3OD): 97.6 (C-1), 153.9 (C-3), 114.7 (C-4),
76.6 (C-5), 47.1 (C-6), 126.9 (C-7), 142.1 (C-8), 56.7 (C-9), 61.1 (C-10), 168.2 (C-11), 51.7 (OMe), 100.2 (C-1),
74.5 (C-2), 77.4 (C-3), 71.5 (C-4), 75.7 (C-5), 64.5 (C-6), 176.5 (C-1), 13.6 (C-2), 8.9 (C-3), 8.8 (C-4).
Pithecoctenium crucigerum (Bignoniaceae).44)
10-O-p-Hydroxybenzoyltheviridoside
C24H28O13: 524.1529; pale yellow amorphous solid; [a ]D25 31.8 (c1.0, MeOH); UV (MeOH): 325 (3.32), 253
(3.91), 201 (4.22); 1H-NMR (500 MHz, CD3OD): 5.58 (d, 5.9, H-1), 7.51 (s, H-3), 2.88 (br s, H2-6), 5.86 (d, 1.5,
H-7), 3.09 (dd, 5.9, 1.0, H-9), 4.93 (d, 2.4, H2-10), 3.73 (s, OMe), 4.64 (d, 8.3, H-1), 3.23 (dd, 9.3, 7.8, H-2),
3.37 (t, 9.3, H-3), 3.28 (m, H-4), 3.27 (m, H-5), 3.83 (dd, 12.0, 1.2, H-6), 3.63 (dd, 11.7, 5.3, H-6), 7.91 (d,
8.8, H-2, 6), 6.83 (d, 8.8, H-3, 5); 13C-NMR (125 MHz, CD3OD): 97.6 (C-1), 154.0 (C-3), 114.6 (C-4), 76.5
(C-5), 47.3 (C-6), 130.1 (C-7), 137.3 (C-8), 57.4 (C-9), 63.3 (C-10), 167.9 (C-11), 51.6 (OMe), 100.3 (C-1), 74.6
(C-2), 77.7 (C-3), 71.5 (C-4), 78.4 (C-5), 62.8 (C-6), 120.7 (C-1), 132.9 (C-2, 6), 116.2 (C-3, 5), 162.0
(C-4), 167.9 (C-7). Pithecoctenium crucigerum (Bignoniaceae).44)
August 2009
81.
82.
83.
84.
85.
86.
87.
777
10-O-Vanilloyltheviridoside
C25H30O14: 554.1635; pale yellow amorphous solid; [a ]D25 26.6 (c2.0, MeOH); UV (MeOH): 327 (3.46), 292
(3.68), 254 (3.85), 220 (4.16), 202 (4.31); 1H-NMR (500 MHz, CD3OD): 5.62 (d, 5.9, H-1), 7.51 (s, H-3), 2.89 (br s,
H2-6), 5.87 (d, 1.5, H-7), 3.10 (d, 5.9, H-9), 4.94 (s, H2-10), 3.73 (s, OMe), 4.64 (d, 8.3, H-1), 3.23 (m, H-2), 3.36 (t,
9.3, H-3), 3.28 (m, H-4), 3.27 (m, H-5), 3.82 (m, H-6), 3.63 (dd, 12.0, 5.1, H-6), 7.58 (d, 1.9, H-2), 6.86 (d, 8.3, H5), 7.60 (dd, 8.3, 1.9, H-6), 3.90 (s, MeO-3); 13C-NMR (125 MHz, CD3OD): 97.5 (C-1), 154.0 (C-3), 114.6 (C-4),
76.5 (C-5), 47.3 (C-6), 130.4 (C-7), 137.2 (C-8), 57.5 (C-9), 63.5 (C-10), 167.9 (C-11), 51.7 (OMe), 100.3 (C-1), 74.6
(C-2), 77.7 (C-3), 71.5 (C-4), 78.2 (C-5), 62.8 (C-6), 122.5 (C-1), 113.8 (C-2), 148.9 (C-3), 152.8 (C-4), 116.1
(C-5), 125.3 (C-6), 168.2 (C-7), 56.5 (MeO-3). Pithecoctenium crucigerum (Bignoniaceae).44)
4-O-[(E)-p-Coumaroyl]-gentiobiosylgenipin
C32H40O17: 696.2265; pale yellow powder; [a ]D22 7.1 (c0.25, MeOH); UV (MeOH): 311 (4.02), 232
(4.24); IR (KBr): 3411, 2923, 1697, 1631, 1604, 1514, 1439, 1375, 1282, 1163, 1075, 896, 833, 768, 532;
1
H-NMR (500 MHz, C5D5N): 5.87 (d, 7.4, H-1), 7.75 (s, H-3), 3.453.40 (m, H-5), 3.05 (dd, 16.8, 8.2,
H-6), 2.61 (br d, 16.8, H-6), 6.31 (s, H-7), 3.11 (dd, 7.5, 7.5, H-9), 4.95 (d, 14.8, H-10), 4.77 (d, 14.8, H10), 3.68 (s, OMe), 5.39 (d, 7.9, H-1), 4.254.27 (m, H-2), 4.084.11 (m, H-3), 4.234.25 (m, H4), 3.953.99 (m, H-5), 4.85 (dd, 11.0, 1.9, H-6), 4.32 (dd, 11.0, 6.0, H-6), 5.27 (d, 7.8, H-1) 4.14
4.17 (m, H-2), 4.474.51 (m, H-3), 5.84 (dd, 9.4, 9.4, H-4), 4.244.25 (m, H-5), 4.32 (dd, 12.4, 4.9,
H-6), 4.27 (dd, 11.3, 2.0, H-6), 7.61 (dd, 8.6, 1.3, H-2, 6), 7.24 (dd, 8.6, 1.3, H-3, 5), 8.02 (d, 15.8,
H-7), 6.64 (d, 15.8, H-8); 13C-NMR (125 MHz, C5D5N): 98.3 (C-1), 152.5 (C-3), 111.7 (C-4), 35.9 (C5), 39.3 (C-6), 127.3 (C-7), 145.6 (C-8), 47.0 (C-9), 61.0 (C-10), 167.8 (C-11), 51.1 (OMe), 101.2 (C-1),
78.4 (C-2), 74.8 (C-3), 78.3 (C-4), 71.8 (C-5), 70.0 (C-6), 105.2 (C-1), 75.6 (C-2), 75.9 (C-3), 72.9
(C-4), 76.4 (C-5), 62.4 (C-6), 126.2 (C-1), 130.9 (C-2, 6), 116.9 (C-3, 5), 161.6 (C-4), 145.8 (C7), 115.2 (C-8), 167.3 (C-9). Gardenia jasminoides (Rubiaceae).40)
Hedycoryside A
2921, 2851, 1713, 1633, 1452, 1385, 1273, 1158, 1073, 716; 1H-NMR (500 MHz, CD3OD): 5.24 (d, 7.8, H-1), 7.52
(br s, H-3), 3.24 (br t, 8.0, H-5), 2.15 (dd, 16.6, 8.0, H-6), 2.89 (dd, 16.6, 8.0, H-6), 5.94 (br s, H-7), 2.84 (br t, 7.8, H-9),
5.07 (br d, 13.6, H-10), 5.01 (br d, 13.6, H-10), 3.71 (s,OMe), 4.72 (d, 7.8, H-1), 3.24 (t, 9.0, H-2), 3.383.35 (m, H3), overlapped (H-4, 5), 3.84 (br d, 11.5, H-6), 3.63 (dd, 11.5, 5.3, H-6), 8.04 (dd, 7.8, 1.3, H-2, 6), 7.48 (t, 7.8, H3, 5), 7.60 (br t, 7.8, H-4); 13C-NMR (125 MHz, CD3OD): 98.7 (C-1), 153.7 (C-3), 112.7 (C-4), 36.8 (C-5), 40.3 (C6), 131.8 (C-7), 139.9 (C-8), 47.9 (C-9), 64.6 (C-10), 169.7 (C-11), 52.0 (OMe), 100.9 (C-1), 75.2 (C-2), 78.3 (C-3),
71.8 (C-4), 78.7 (C-5), 63.1 (C-6), 131.8 (C-1), 130.9 (C-2, 6), 129.9 (C-3, 5), 134.6 (C-4), 168.2 (C-7). Hedyotis corymbosa (Rubiaceae).32)
Eucomoside B
C25H31NO11: 521.1897; white powder; [a ]D 10.6 (c0.1, MeCN); 1H-NMR (500 MHz, CD3OD): 5.10
(d, 7.3, H-1), 7.14 (d, 1.2, H-3), 3.20 (m, H-5), 1.88 (dd, 15.9, 7.9, H-6), 2.50 (dd, 15.3, 7.9, H-6), 5.69 (s,
H-7), 2.72 (d, 9.2, 9.2, H-9), 4.16 (d, 14.0, H-10), 4.29 (d, 14.0, H-10), 4.69 (d, 7.3, H-1), 3.27 (m, H-2),
3.39 (dd, 9.2, 9.2, H-3), 3.27 (m, H-4, 5), 3.65 (dd, 12.2, 1.8, H-6), 3.85 (dd, 12.2, 1.8, H-6), 7.20 (s,
H-2, 6), 7.21 (s, H-3, 5), 7.17 (s, H-4), 3.09 (dd, 14.0, 7.3, H-7), 3.27 (m, H-7), 4.60 (m, H-8); 13CNMR (125 MHz, CD3OD): 97.8 (C-1), 148.6 (C-3), 115.8 (C-4), 36.2 (C-5), 39.2 (C-6), 127.9 (C-7),
144.8 (C-8), 47.4 (C-9), 61.4 (C-10), 168.9 (C-11), 100.3 (C-1), 74.9 (C-2), 77.8 (C-3), 71.6 (C-4),
78.3 (C-5), 62.7 (C-6), 139.8 (C-1), 130.7 (C-2, 6), 129.2 (C-3, 5), 127.4 (C-4), 38.7 (C-7), 56.7
(C-8), 177.0 (C-9). Eucommia ulmoides (Eucommiaceae).45)
Eucomoside C
C27H32N2O11: 560.2006; white powder; [a ]D 13.1 (c0.5, H2O); 1H-NMR (500 MHz, CD3OD):
5.06 (d, 7.3, H-1), 7.11 (s, H-3), 3.13 (m, H-5), 1.63 (dd, 15.9, 7.9, H-6), 2.24 (dd, 15.3, 7.9, H-6), 5.58
(s, H-7), 2.67 (dd, 9.2, 9.2, H-9), 4.12 (d, 14.7, H-10), 4.29 (d, 14.7, H-10), 4.65 (d, 7.9, H-1), 3.20 (m,
H-2), 3.37 (m, H-3), 3.27 (m, H-4, 5), 3.63 (dd, 11.6, 5.5, H-6), 3.84 (dd, 12.2, 1.8, H-6), 7.09 (s,
H-2), 7.57 (d, 7.9, H-4), 6.98 (dd, 7.9, 7.3, H-5, 6), 7.30 (d, 8.6, H-7), 3.20 (m, H-10), 3.43 (dd,
14.7, 4.3, H-10), 4.61 (d, 6.7, H-11); 13C-NMR (125 MHz, CD3OD): 97.7 (C-1), 150.2 (C-3), 115.5
(C-4), 36.0 (C-5), 38.8 (C-6), 127.9 (C-7), 144.7 (C-8), 47.4 (C-9), 61.3 (C-10), 169.9 (C-11), 100.3
(C-1), 74.9 (C-2), 77.9 (C-3), 71.6 (C-4), 78.4 (C-5), 62.7 (C-6), 124.4 (C-2), 111.8 (C-3), 119.6
(C-4), 119.8 (C-5), 122.4 (C-6), 112.2 (C-7), 129.0 (C-8), 138.1 (C-9), 28.3 (C-10), 57.5 (C-11),
180.0 (C-12). Eucommia ulmoides (Eucommiaceae).45)
Hedycoryside B
C24H28O12: 508.1580; amorphous powder; [a ]D24 7.5 (c0.65, MeOH); UV (MeOH): 252 (4.20); IR (KBr):
3420, 2923, 1699, 1633, 1609, 1441, 1385, 1275, 1166, 1100, 1043, 758; 1H-NMR (500 MHz, acetone-d6): 5.25
(d, 7.5, H-1), 7.49 (br s, H-3), overlapped (H-5), 2.14 (dd, 16.5, 7.8, H-6), 2.87 (dd, 16.5, 7.8, H-6), 5.91 (br s,
H-7), 2.83 (br t, 7.5, H-9), 5.08 (br d, 14.0, H-10), 4.93 (br d, 14.0, H-10), 3.69 (s, OMe), 4.77 (d, 7.8, H-1),
3.29 (t, 8.6, H-2), 3.47 (t, 8.6, H-3), 3.40 (t, 8.6, H-4), 3.383.36 (m, H-5), 3.82 (dd, 11.9, 2.5, H-6), 3.66
(dd, 11.9, 5.8, H-6), 7.94 (d, 8.8, H-2, 6), 6.93 (d, 8.8, H-3, 5); 13C-NMR (125 MHz, acetone-d6): 97.9 (C1), 152.5 (C-3), 112.1 (C-4), 35.9 (C-5), 39.5 (C-6), 130.2 (C-7), 139.7 (C-8), 47.3 (C-9), 63.2 (C-10), 168.0
(C-11), 51.4 (OMe), 100.5 (C-1), 74.5 (C-2), 77.6 (C-3), 71.1 (C-4), 77.8 (C-5), 62.6 (C-6), 122.1 (C-1),
132.6 (C-2, 6), 116.1 (C-3, 5), 163.0 (C-4), 166.7 (C-7). Hedyotis corymbosa (Rubiaceae).32)
Teneoside B
1685, 1630, 1307, 1020; 1H-NMR (500 MHz, D2O): 5.38 (d, 5.1, H-1), 7.48 (d, 0.86, H-3), 3.21 (t, 6.3, H-5), 4.58 (t,
1.9, H-6), 5.81 (t, 1.8, H-7), 3.05 (m, H-9), 4.88 (s, H2-10), 3.75 (s, OMe), 4.80 (d, 8.0, H-1), 3.27 (dd, 9.1, 7.9, H-2),
3.36 (t, 9.1, H-3), 3.23 (t, 9.1, H-4), 3.33 (m, H-5), 3.65 (dd, 12.0, 6.7, H-6), 3.94 (dd, 12.4, 2.2, H-6), 5.10 (d, 1.7,
H-1), 3.86 (dd, 3.7, 2.0, H-2), 3.81 (dd, 9.3, 3.7, H-3), 3.52 (t, 9.5, H-4), 3.91 (dd, 10.0, 6.2, H-5), 1.21 (d, 6.2, H36); 13C-NMR (125 MHz, D2O): 98.7 (C-1), 153.8 (C-3), 112.5 (C-4), 43.5 (C-5), 81.8 (C-6), 133.5 (C-7), 147.8 (C-8),
48.5 (C-9), 71.8 (C-10), 172.1 (C-11), 54.4 (OMe), 102.2 (C-1), 75.4 (C-2), 79.6 (C-3), 72.4 (C-4), 78.8 (C-5), 63.5
(C-6), 102.1 (C-1), 72.3 (C-2, 3), 73.8 (C-4), 70.2 (C-5), 18.0 (C-6). Hedyotis tenelliflora (Rubiaceae).46)
778
88.
89.
90.
91.
92.
93.
94.
Vol. 57, No. 8

6-O-[(E)-Caffeoyl]-deacetylasperulosidic acid methyl ester
C26H30O14: 566.1762; pale yellow powder; [a ]D 7.4 (c0.25, MeOH); UV (MeOH): 324 (4.46), 234 (4.26); IR
(KBr): 3426, 2924, 1693, 1632, 1522, 1441, 1384, 1279, 1162, 1077, 896, 787, 555; 1H-NMR (500 MHz, CD3OD):
5.00 (d, 8.9, H-1), 7.55 (s, H-3), 2.952.96 (m, H-5), 4.70 (d, 15.6, H-6), 2.61 (br d, 16.8, H-6), 5.95 (s, H-7), 2.56
(dd, 8.1, 8.1, H-9), 4.99 (dd, 9.0, 4.4, H-10), 4.77 (dd, 9.0, 4.4, H-10), 3.64 (s, OMe), 4.64 (d, 7.8, H-1), 3.143.18
(m, H-2, 3, 4), 3.303.31 (m, H-5), 3.77 (dd, 12.3, 1.9, H-6), 3.56 (dd, 12.3, 5.1, H-6), 6.96 (d, 1.3, H-2), 6.70
(d, 8.2, H-5), 6.87 (dd, 8.2, 1.3, H-6), 7.49 (d, 15.8, H-7), 6.21 (d, 15.8, H-8); 13C-NMR (125 MHz, CD3OD):
101.7 (C-1), 155.6 (C-3), 108.3 (C-4), 42.6 (C-5), 75.6 (C-6), 132.0 (C-7), 146.4 (C-8), 46.6 (C-9), 63.9 (C-10),
169.6 (C-11), 51.2 (OMe), 101.0 (C-1), 75.2 (C-2), 78.7 (C-3), 71.7 (C-4), 78.1 (C-5), 63.2 (C-6), 127.9 (C-1),
115.5 (C-2), 147.0 (C-3), 149.9 (C-4), 116.8 (C-5), 123.3 (C-6), 147.6 (C-7), 115.1 (C-8), 169.1 (C-9). Gardenia jasminoides (Rubiaceae).40)
10-O-p-Coumaroyl-10-O-deacetyldaphylloside
C26H30O13: 550.1686; white powder; [a ]D20 5.0 (c0.23, MeOH); UV (MeOH): 316.5 (0.75), 225.8 (0.71); IR
(KBr): 3427, 2922, 1695, 1633, 1604, 1516, 1440, 1275, 1169, 1076, 833, 519; 1H-NMR (300 MHz, DMSO-d6):
4.99 (d, 9.0, H-1), 7.63 (s, H-3), 2.91 (t, 6.6, H-5), 4.64 (br d, 6.0, H-6), 6.00 (br s, H-7), 2.55 (t, 7.8, H-9), 4.80 (br d,
15.3, H-10), 4.90 (br d, 15.3, H-10), 3.20 (OMe), 4.59 (d, 8.1, H-1), 3.023.22 (m, H-2, 3, 4, 5), 3.43 (dd, 11.9,
4.8, H-6), 3.643.66 (m, H-6), 7.547.58 (m, H-2, 6), 6.79 (d, 9.0, H-3, 5), 7.587.62 (m, H-7), 6.44 (d,
15.9, H-8); 13C-NMR (75 MHz, DMSO-d6): 99.6 (C-1), 153.2 (C-3), 107.2 (C-4), 40.8 (C-5), 73.2 (C-6), 131.8 (C7), 143.0 (C-8), 44.8 (C-9), 61.0 (C-10), 166.9 (C-11), 51.2 (OMe), 99.1 (C-1), 73.4 (C-2), 76.6 (C-3), 69.9 (C4), 77.2 (C-5), 62.0 (C-6), 125.1 (C-1), 130.5 (C-2, 6), 115.9 (C-3, 5), 160.1 (C-4), 145.1 (C-7), 113.9 (C8), 166.3 (C-9). Daphniphyllum angustifolium (Daphniphyllaceae).47)
10-O-p-Coumaroyl-10-O-deacetyl-11-demethoxy-11-ethoxydaphylloside
C27H32O13: 564.1842; white powder; [a ]D20 7.0 (c0.24, MeOH); UV (MeOH): 316.2 (0.74), 225.0
(0.70);1H-NMR (300 MHz, CD3OD): 5.09 (d, 9.0, H-1), 7.63 (s, H-3), 3.02 (t, 6.6, H-5), 4.78 (br d, 6.0, H6), 6.03 (br s, H-7), 2.65 (t, 8.1, H-9), 4.784.82 (m, H-10), 5.08 (d, 15.3, H-10), 4.17 (q, 7.2, H2-12), 1.27
(t, 7.2, H3-13), 4.72 (d, 7.2, H-1), 3.233.39 (m, H-2, 3, 4, 5), 3.57 (dd, 6.9, 2.0, H-6), 3.84 (d, 12.0, H6), 7.45 (d, 9.0, H-2, 6), 6.78 (d, 9.0, H-3, 5), 7.63 (d, 16.2, H-7), 6.35 (d, 16.2, H-8); 13C-NMR
(75 MHz, CD3OD): 101.5 (C-1), 155.4 (C-3), 108.5 (C-4), 42.6 (C-5), 75.0 (C-6), 131.8 (C-7), 146.3 (C-8),
48.3 (C-9), 61.4 (C-10), 169.0 (C-11), 63.8 (C-12), 14.7 (C-13), 100.8 (C-1), 75.6 (C-2), 77.9 (C-3), 71.6
(C-4), 78.7 (C-5), 63.1 (C-6), 127.1 (C-1), 131.4 (C-2, 6), 117.1 (C-3, 5), 161.7 (C-4), 147.2 (C-7),
114.9 (C-8), 168.9 (C-9). Daphniphyllum angustifolium (Daphniphyllaceae).47)
10-O-Benzoyl-10-O-deacetyldaphylloside
C24H28O12: 508.1580; white powder; [a ]D20 3.0 (c0.09, MeOH); UV (MeOH): 232 (1.36), 202 (0.63); 1H-NMR
(300 MHz, DMSO-d6): 5.14 (d, 5.1, H-1), 7.66 (s, H-3), 2.94 (t, 6.6, H-5), 4.74 (d, 6.0, H-6), 6.08 (s, H-7), 2.61 (t, 8.1, H9), 4.99 (d, 15.3, H-10), 5.04 (d, 15.3, H-10), 3.35 (s, OMe), 4.59 (d, 7.5, H-1), 2.983.19 (m, H-2, 3, 4, 5), 3.39
3.42 (m, H-6), 3.603.64 (m, H-6), 8.03 (d, 7.2, H-2, 6), 7.55 (t, 7.2, H-3, 5), 7.66 (t, 7.2, H-4); 13C-NMR (75 MHz,
DMSO-d6): 99.6 (C-1), 153.2 (C-3), 107.2 (C-4), 40.7 (C-5), 73.4 (C-6), 131.9 (C-7), 142.7 (C-8), 44.8 (C-9), 61.0 (C10), 166.9 (C-11), 51.1 (OMe), 99.1 (C-1), 73.4 (C-2), 76.5 (C-3), 69.9 (C-4), 77.2 (C-5), 62.8 (C-6), 129.6 (C-1),
129.4 (C-2, 6), 128.9 (C-3, 5), 133.5 (C-4), 165.4 (C-7). Daphniphyllum angustifolium (Daphniphyllaceae).47)
10-O-Benzoyl-10-O-deacetyl-11-demethoxy-11-ethoxydaphylloside
C25H30O12: 522.1737; white powder; [a ]D20 9.0 (c0.16, MeOH); UV (MeOH): 231.8 (1.18), 204.0 (0.73); 1HNMR (300 MHz, CD3OD): 5.10 (d, 9.0, H-1), 7.64 (d, 1.2, H-3), 3.07 (t, 6.6, H-5), 4.784.82 (m, H-6), 6.09
(br s, H-7), 2.68 (t, 8.1, H-9), 5.01 (br d, 15.3, H-10), 5.22 (br d, 15.3, H-10), 4.17 (q, H2-12), 1.27 (t, 7.2, H3-13),
4.73 (d, 7.2, H-1), 3.233.40 (m, H-2), 3.023.22 (m, H-3, 4, 5), 3.60 (dd, 12.0, 5.4, H-6), 3.86 (d, 12.0, H6), 8.04 (d, 7.2, H-2, 6), 7.48 (t, 7.2, H-3, 5), 7.60 (t, 7.2, H-4); 13C-NMR (75 MHz, CD3OD): 101.5 (C-1),
155.4 (C-3), 108.5 (C-4), 42.6 (C-5), 75.0 (C-6), 131.4 (C-7), 146.1 (C-8), 46.6 (C-9), 61.4 (C-10), 169.1 (C-11),
64.4 (C-12), 14.7 (C-13), 100.8 (C-1), 75.6 (C-2), 78.0 (C-3), 71.6 (C-4), 78.7 (C-5), 63.1 (C-6), 131.4 (C1), 130.8 (C-2, 6), 129.8 (C-3, 5), 134.6 (C-4), 167.8 (C-7). Daphniphyllum angustifolium (Daphniphyllaceae).47)
11-Demethoxy-11-ethoxydaphylloside
C20H28O12: 460.1580; white powder; [a ]D20 10.0 (c0.20, MeOH); UV: 233 (0.53), 203 (0.46); 1H-NMR
(300 MHz, CD3OD): 5.06 (d, 9.0, H-1), 7.65 (d, 1.2, H-3), 3.05 (t, 8.1, H-5), 4.774.87 (m, H-6), 6.02 (br s, H-7),
2.63 (t, 8.1, H-9), 4.774.87 (m, H-10), 4.94 (d, 15.3, H-10), 4.17 (q, 7.2, H2-12), 1.27 (t, 7.2, H3-13), 4.72 (d, 7.5,
H-1), 3.233.39 (m, H-2, 3, 4, 5), 3.61 (dd, 11.7, 5.7, H-6), 3.84 (d, 11.7, H-6), 2.08 (s, Ac); 13C-NMR
(75 MHz, CD3OD): 101.4 (C-1), 155.3 (C-3), 108.5 (C-4), 42.5 (C-5), 75.0 (C-6), 131.9 (C-7), 146.0 (C-8), 46.3 (C9), 61.4 (C-10), 172.6 (C-11), 63.9 (C-12), 14.7 (C-13), 100.7 (C-1), 75.6 (C-2), 78.0 (C-3), 71.6 (C-4), 78.7 (C5), 63.1 (C-6), 20.9, 169.0 (Ac). Daphniphyllum angustifolium (Daphniphyllaceae).47)
10-O-Dihydroferuloyl-10-O-deacetyldaphylloside
C27H34O14: 582.1948; isolated as hexaacetate; white amorphous powder; UV (MeOH): 324 (3.20), 302
(3.04), 280 (3.32), 236 (3.96); IR (KBr): 1750, 1640, 1605, 1503, 1040, 908; 1H-NMR (400 MHz, CDCl3):
4.82 (d, 8.0, H-1), 7.52 (d, 1.0, H-3), 3.28 (dd, 8.0, 8.0, H-5), 5.56 (dd, 8.0, 2.0, H-6), 6.05 (d, 2.0, H-7), 2.85
(dd, 8.0, 8.0, H-9), 4.92 (br s, H2-10), 3.73 (s, OMe), 4.97 (d, 8.0, H-1), 4.98 (dd, 8.5, 8.0, H-2), 5.24 (dd,
9.0, 8.5, H-3), 5.08 (dd, 9.0, 9.0, H-4), 3.76 (m, H-5), 4.14 (dd, 12.5, 2.5, H-6), 4.32 (dd, 12.5, 4.5, H-6),
7.50 (d, 2.0, H-2), 7.02 (d, 8.0, H-5), 7.56 (dd, 8.0, 2.0, H-6), 2.84 (t, 7.0, H-7), 2.34 (t, 7.0, H-8), 3.82
(s, MeO-3), 1.96, 1.99, 2.06, 2.07, 2.08, 2.26 (each s, 6Ac); 13C-NMR (100 MHz, CDCl3): 95.8 (C-1),
154.0 (C-3), 106.9 (C-4), 42.5 (C-5), 75.7 (C-6), 131.5 (C-7), 150.0 (C-8), 46.7 (C-9), 62.3 (C-10), 169.3
(C-11), 52.0 (OMe), 97.5 (C-1), 70.6 (C-2), 72.5 (C-3), 68.2 (C-4), 72.1 (C-5), 61.7 (C-6), 136.9 (C1), 112.2 (C-2), 149.8 (C-3), 147.7 (C-4), 116.3 (C-5), 122.2 (C-6), 29.6 (C-7), 38.5 (C-8), 168.6 (C9), 56.2 (MeO-3), 20.62, 20.7, 20.8, 20.9, 21.1, 169.4, 169.5, 169.6, 170.7, 171.3, 171.6 (6Ac). Wendlandia tinctoria (Rubiaceae).35)
August 2009
95.
779
Eucomoside A
C18H22O11: 414.1162; white powder; [a ]D 99.1 (c0.1, MeOH); 1H-NMR (500 MHz, C5D5N): 5.67 (d, 1.2, H-1), 5.87
(d, 2.4, H-3), 3.54 (dd, 12.8, 2.5, H-4), 3.72 (m, H-5), 5.90 (s, H-7), 3.30 (d, 8.5, H-9), 4.78 (d, 14.7, H-10), 4.85 (d, 14.7,
H-10), 2.07 (s, OAc), 5.32 (d, 7.3, H-1), 4.03 (m, H-2), 4.29 (dd, 9.2, 8.6, H-3), 4.23 (dd, 9.2, 9.2, H-4), 4.03 (m, H-5),
4.39 (dd, 11.6, 5.5, H-6), 4.60 (dd, 12.2, 2.1, H-6); 13C-NMR (125 MHz, C5D5N): 91.9 (C-1), 95.8 (C-3), 38.3 (C-4), 35.3
(C-5), 86.9 (C-6), 129.3 (C-7), 143.7 (C-8), 45.5 (C-9), 61.0 (C-10), 178.5 (C-11), 20.5, 170.3 (OAc), 99.0 (C-1), 80.3 (C2), 75.8 (C-3), 71.2 (C-4), 79.9 (C-5), 62.6 (C-6). Eucommia ulmoides (Eucommiaceae).45)
7-Deoxyloganic acid-b -D-glucopyranosyl ester

C22H34O14: 522.1948; amorphous powder; [a ]D25 37.8 (c0.138, MeOH); UV (MeOH): 238 (4.0); 1H-NMR (400 MHz,
CD3OD): 5.26 (d, 5.5, H-1), 7.51 (d, 1.1, H-3), 2.90 (m, H-5), 1.44 (m, Ha -6), 2.22 (m, Hb -6), 1.87 (m, Ha -7), 1.20 (m, Hb -7),
1.98 (m, H-8), 1.76 (m, H-9), 1.10 (d, 7.0, H3-10), 4.67 (d, 8.0, H-1), 3.20 (dd, 9.2, 8.0, H-2), 3.653.70 (m, Ha-6, 6), 3.84
(dd, 11.7, 2.2, Hb-6), 5.51 (d, 8.1, H-1), 3.89 (dd, 11.7, 2.0, Hb-6); 13C-NMR (100 MHz, CD3OD): 98.0 (C-1), 154.2 (C3),112.3 (C-4), 35.1 (C-5), 33.2 (C-6), 34.2 (C-7), 36.5 (C-8), 49.6 (C-9), 20.8 (C-10), 167.7 (C-11), 100.2 (C-1), 74.8 (C-2),
78.1 (C-3), 71.6 (C-4), 78.8 (C-5, 5), 62.8 (C-6), 95.4 (C-1), 74.0 (C-2), 78.4 (C-3), 71.1 (C-4), 62.3 (C-6). Hydrangea
macrophylla (Saxifragaceae).48)
97. Loganic acid 11-O-b -glucopyranosyl ester
C22H34O15: 538.1897; white amorphous powder; [a ]D28 50.0 (c0.1, MeOH); IR (KBr): 3427, 1719, 1640, 1288, 1076;
1
H-NMR (400 MHz, CD3OD): 5.36 (d, 4.0, H-1), 7.60 (s, H-3), 3.09 (m, H-5), 1.88 (ddd, 14.0, 4.8, 2.4, H-6), 2.21 (ddd,
14.0, 8.0, 6.0, H-6), 4.16 (m, H-7), 1.75 (ddq, 13.6, 9.6, 6.8, H-8), 2.14 (ddd, 9.6, 4.0, 3.6, H-9), 1.10 (d, 6.8, H3-10), 4.89
(d, 7.9, H-1), 3.24 (m, H-2), 3.49 (m, H-3), 3.363.42 (m, H-4, 5), 3.93 (dd, 14.4, 6.0, H-6), 3.73 (dd, 14.4, 4.4, H6), 5.51 (d, 8.0, H-1), 3.363.42 (m, H-2), 3.49 (m, H-3), 3.363.42 (m, H-4, 5), 3.83 (dd, 12.0, 6.0, H-6), 3.90
(dd, 12.0, 2.0, H-6); 13C-NMR (100 MHz, CD3OD): 97.8 (C-1), 154.0 (C-3), 113.3 (C-4), 31.4 (C-5), 42.1 (C-6), 75.1 (C7), 44.8 (C-8), 46.3 (C-9), 13.2 (C-10), 168.0 (C-11), 99.8 (C-1), 75.1 (C-2), 78.4 (C-3), 71.2 (C-4), 78.0 (C-5), 62.3
(C-6), 95.2 (C-1), 74.3 (C-2), 78.4 (C-3), 70.7 (C-4), 77.2 (C-5), 62.0 (C-6). Gentiana rhodantha (Gentianaceae).49)
98. Teneoside A (10-O-(a -L-Rhamnopyranosyl) deacetylasperuloside)
2930, 1755, 1650, 1070; 1H-NMR (500 MHz, D2O): 5.82 (d, 1.8, H-1), 7.31 (d, 2.8, H-3), 3.55 (d, 3.6, H-5), 5.60 (m, H-6),
5.68 (m, H-7), 3.33 (m, H-9), 4.56 (s, H2-10), 4.76 (d, 8.2, H-1), 3.27 (dd, 9.3,7.9, H-2), 3.40 (t, 9.1, H-3), 3.25 (t, 9.1,
H-4), 3.34 (m, H-5), 3.67 (dd, 11.9, 6.7, H-6), 3.94 (dd, 11.9, 2.1, H-6), 5.10 (d, 1.8, H-1), 3.93 (dd, 3.5, 1.8, H-2),
3.67 (dd, 9.5, 3.3, H-3), 3.64 (t, 9.8, H-4), 3.81 (dd, 10.5, 6.2, H-5), 1.21 (d, 6.2, H3-6); 13C-NMR (125 MHz, D2O):
95.7 (C-1), 152.3 (C-3), 107.4 (C-4), 38.6 (C-5), 88.5 (C-6), 127.0 (C-7), 149.1 (C-8), 45.1 (C-9), 70.9 (C-10), 174.5 (C11), 102.5 (C-1), 75.8 (C-2), 79.5 (C-3), 71.9 (C-4), 78.5 (C-5), 63.6 (C-6), 102.0 (C-1), 72.1 (C-2, 3), 73.9 (C-4),
70.3 (C-5), 18.0 (C-6). Hedyotis tenelliflora (Rubiaceae).46)
99. 10-O-Coumaroyl-10-O-deacetylasperuloside
C25H26O12: 518.1424; white powder; [a ]D20 96.1 (c0.60, MeOH); UV (MeOH): 312.5 (3.08), 222.8 (3.25); IR
(KBr): 3411, 2923, 1739, 1656, 1604, 1516, 1261, 1168, 1074, 1020, 982, 833; 1H-NMR (300 MHz, CD3OD): 6.04
(br s, H-1), 7.29 (s, H-3), 3.333.40 (m, H-5), 5.55 (br d, 6.0, H-6), 5.77 (s, H-7), 3.223.27 (m, H-9), 4.76 (br d,
14.3, H-10), 4.89 (br d, 14.3, H-10), 4.72 (d, 7.8, H-1), 3.303.47 (m, H-2, 3, 4, 5), 3.64 (dd, 12.0, 6.3, H-6),
3.86 (d, 12.0, H-6), 7.54 (d, 8.4, H-2, 6), 6.87 (d, 8.4, H-3, 5), 7.65 (d, 15.9, H-7), 6.37 (d, 15.9, H-8); 13C-NMR
(75 MHz, CD3OD): 93.5 (C-1), 150.5 (C-3), 106.2 (C-4), 37.4 (C-5), 86.4 (C-6), 129.1 (C-7), 144.5 (C-8), 45.9 (C9), 61.8 (C-10), 173.0 (C-11), 100.1 (C-1), 74.7 (C-2), 77.9 (C-3), 71.6 (C-4), 78.4 (C-5), 62.8 (C-6), 127.1 (C1), 131.5 (C-2, 6), 117.0 (C-3, 5), 161.5 (C-4), 147.4 (C-7), 114.6 (C-8), 168.6 (C-9). Daphniphyllum angustifolium (Daphniphyllaceae).47)
100. 10-O-Benzoyl-10-O-deacetylasperuloside
C23H24O11: 476.1318; white powder; [a ]D20 88.0 (c0.07, MeOH); UV (MeOH): 231.0 (1.80), 202.5 (1.25); 1H-NMR
(300 MHz, CD3OD): 6.06 (br s, H-1), 7.31 (d, 1.8, H-3), 3.293.32 (m, H-5), 5.58 (br d, 6.0, H-6), 5.82 (s, H-7), 3.17
3.21 (m, H-9), 4.90 (d, 13.8, H-10), 5.03 (d, 13.8, H-10), 4.68 (d, 8.1, H-1), 3.183.40 (m, H-2, 3, 4, 5), 3.71 (d,
12.0, H-6), 3.86 (d, 12.0, H-6), 8.03 (d, 7.2, H-2, 6), 7.49 (t, 7.2, H-3, 5), 7.61 (t, 7.2, H-4); 13C-NMR (75 MHz,
CD3OD): 93.6 (C-1), 150.4 (C-3), 106.4 (C-4), 37.6 (C-5), 86.4 (C-6), 129.5 (C-7), 144.4 (C-8), 45.6 (C-9), 62.7 (C-10),
172.7 (C-11), 100.2 (C-1), 74.7 (C-2), 77.9 (C-3), 71.6 (C-4), 78.4 (C-5), 62.8 (C-6), 131.0 (C-1), 130.8 (C-2, 6),
129.8 (C-3, 5), 134.7 (C-4), 167.5 (C-7). Daphniphyllum angustifolium (Daphniphyllaceae).47)
96.
101.
Wendoside
102.
C16H24O10: 376.1369; isolated as pentaacetate; white amorphous powder; IR (KBr): 1755, 2856, 1128; 1H-NMR
(400 MHz, CDCl3): 5.30 (d, 2.5, H-1), 6.54 (br s, H-3), 2.32 (m, H-4), 3.06 (m, H-5), 5.04 (dd, 7.5, 1.2, H-6), 3.82 (br s,
H-7), 2.62 (m, H-9), 1.23 (s, H3-10), 3.84 (dd, 11.5, 4.5, H-11), 3.92 (dd, 11.5, 2.5, H-11), 4.73 (d, 7.5, H-1), 5.22 (dd,
8.5, 7.5, H-2), 5.24 (dd, 9.0, 8.5, H-3), 5.08 (dd, 9.0, 9.0, H-4), 3.76 (m, H-5), 4.12 (dd, 12.5, 2.5, H-6), 4.24 (dd,
12.5, 4.5, H-6), 2.02, 2.03, 2.04, 2.05, 2.07 (each s, 5Ac); 13C-NMR (100 MHz, CDCl3): 101.3 (C-1), 103.1 (C-3),
31.8 (C-4), 54.3 (C-5), 85.7 (C-6), 56.4 (C-7), 77.5 (C-8), 53.8 (C-9), 29.2 (C-10), 72.0 (C-11), 103.1 (C-1), 71.8 (C2), 73.0 (C-3), 68.5 (C-4), 72.0 (C-5), 62.3 (C-6), 20.62, 20.73, 169.3, 169.42, 170.4, 170.6 (5Ac). Wendlandia tinctoria (Rubiaceae).35)
6-O-b -D-Glucopyranosylphlorigidoside C
C23H34O16: 566.1846; amorphous powder; [a ]D23 53.9 (c0.28, H2O); UV: 239, 205; IR (KBr): 3415, 2897, 1668,
1637, 1443, 1313, 1078, 960, 657; 1H-NMR (400 MHz, CD3OD): 5.26 (d, 9.7, H-1), 7.53 (s, H-3), 2.66 (t-like, 7.8, H-5),
4.09 (dd, 7.8, 1.2, H-6), 3.39 (d, 1.2, H-7), 2.39 (dd, 9.7, 7.5, H-9), 1.54 (s, H3-10), 3.73 (s, OMe), 4.78 (d, 8.0, H-1),
3.23 (H-2, 3, 4), 3.39 (H-3), 3.20 (H-4), 3.513.55 (m, H-5), 3.68 (dd, 12.0, 4.2, H-6), 4.18 (dd, 12.0, 1.8, H-6),
4.34 (d, 7.7, H-1), 3.64 (dd, 11.8, 5.7, H-6), 3.86 (dd, 11.8, 2.3, H-6); 13C-NMR (100 MHz, CD3OD): 97.4 (C-1),
154.7 (C-3), 109.0 (C-4), 38.9 (C-5), 79.7 (C-6), 65.5 (C-7), 63.5 (C-8), 45.6 (C-9), 18.5 (C-10), 171.4 (C-11), 52.7
(OMe), 100.8 (C-1), 75.3 (C-2), 78.4 (C-3), 72.6 (C-4), 78.3 (C-5), 71.2 (C-6), 106.2 (C-1), 75.6 (C-2), 78.7 (C3), 72.2 (C-4), 78.6 (C-5), 63.3 (C-6). Lamiophlomis rotata (Labiatae).50)
780
103.
104.
105.
106.
107.
108.
109.
110.
Vol. 57, No. 8

6-O-a -D-Galactopyranosylphlorigidoside C
1443, 1313, 1078, 960, 557; 1H-NMR (400 MHz, CD3OD): 5.19 (d, 9.7, H-1), 7.54 (s, H-3), 2.66 (t-like, 7.4, H-5), 3.97
(dd, 7.4, 1.1, H-6), 3.36 (d, 1.1, H-7), 2.39 (dd, 9.7, 7.4, H-9), 1.55 (s, H3-10), 3.73 (s, OMe), 4.77 (d, 7.9, H-1), 3.26 (
H-2, 4), 3.40 (H-3), 3.513.55 (m, H-5), 3.83 (H-6), 3.80 (H-6), 4.87 (d, 3.7, H-1), 3.75 (H-2), 3.70 (H-3), 3.86
(H-4), 3.82 (H-5), 3.67 (H2-6); 13C-NMR (100 MHz, CD3OD): 97.6 (C-1), 154.7 (C-3), 109.1 (C-4), 39.0 (C-5), 80.0
(C-6), 65.1 (C-7), 63.5 (C-8), 45.6 (C-9), 18.5 (C-10), 171.3 (C-11), 52.8 (OMe), 101.0 (C-1), 75.3 (C-2), 78.5 (C-3),
72.7 (C-4), 77.3 (C-5), 69.2 (C-6), 100.8 (C-1), 70.7 (C-2), 72.1 (C-3), 71.4 (C-4), 73.0 (C-5), 63.0 (C-6).
Lamiophlomis rotata (Labiatae).50)
6-O-b -D-Glucopyranosylsesamoside
1635, 1387, 1313, 1082, 1034, 606;1H-NMR (400 MHz, CD3OD): 5.43 (d, 9.3, H-1), 7.55 (s, H-3), 4.39 (d, 1.3, H-6),
3.51 (br s, H-7), 2.50 (d, 9.3, H-9), 1.52 (s, H3-10), 3.73 (s, OMe), 4.73 (d, 7.9, H-1), 3.343.20 ( H-2, 4, 3, 4, 5),
3.37 (t-like, 9.0, H-3), 3.503.55 (m, H-5), 4.19 (dd, 12.1, 1.7, H-6), 3.69 (dd, 12.1, 5.2, H-6), 4.33 (d, 7.6, H-1),
3.16 (dd, 8.6, 7.6, H-2), 3.64 (dd, 11.8, 5.7, H-6), 3.86 (dd, 11.8, 1.9, H-6); 13C-NMR (100 MHz, CD3OD): 97.8 (C-1),
155.7 (C-3), 113.3 (C-4), 75.1 (C-5), 78.0 (C-6), 66.3 (C-7), 63.9 (C-8), 54.7 (C-9), 18.3 (C-10), 169.5 (C-11), 52.5
(OMe), 100.6 (C-1), 74.9 (C-2), 78.1 (C-3), 72.3 (C-4), 78.0 (C-5), 71.0 (C-6), 106.0 (C-1), 75.4 (C-2), 78.5 (C3), 72.0 (C-4), 78.4 (C-5), 63.1 (C-6). Lamiophlomis rotata (Labiatae).50)
6-O-a -D-Galactopyranosylsesamoside
1635, 1406, 1313, 1209, 1151, 1082,1030; 1H-NMR (400 MHz, CD3OD): 5.39 (d, 8.8, H-1), 7.56 (s, H-3), 4.31 (d, 1.5,
H-6), 3.48 (br s, H-7), 2.50 (d, 8.8, H-9), 1.51 (s, H3-10), 3.73 (s, OMe), 4.72 (d, 7.9, H-1), 3.25 (dd, 9.0, 7.9, H-2), 3.37
(t-like, 9.0, H-3), 3.29 (H-4 ), 3.503.55 (m, H-5), 3.83 (H-6, 5), 4.87 (d, 3.6, H-1), 3.76 (H-2), 3.70 (H-3), 3.87
(H-4), 3.67 (H2-6); 13C-NMR (100 MHz, CD3OD): 97.7 (C-1), 155.7 (C-3), 113.4 (C-4), 75.3 (C-5), 78.0 (C-6), 66.1
(C-7), 64.0 (C-8), 54.6 (C-9), 18.1 (C-10), 169.4 (C-11), 52.5 (OMe), 100.7 (C-1), 74.9 (C-2), 78.1 (C-3), 72.3 (C-4),
77.1 (C-5), 68.8 (C-6), 100.6 (C-1), 70.6 (C-2), 71.9 (C-3), 71.2 (C-4), 72.8 (C-5), 62.9 (C-6). Lamiophlomis rotata (Labiatae).50)
6-O-b -D-Glucopyranosylbarlerin
1639, 1441, 1383, 1292, 1188, 1082, 864, 611; 1H-NMR (400 MHz, CD3OD): 5.89 (d, 2.7, H-1), 7.43 (d, 1.2, H-3), 3.06
(br d, 8.8, H-5), 4.31 (m, H-6), 2.19 (br d, 14.9, H-7), 2.04 (dd, 14.9, 5.5, H-7), 2.96 (dd, 8.8, 2.7, H-9), 1.52 (s, H3-10),
3.70 (s, OMe), 2.01 (s, Ac), 4.63 (d, 8.0, H-1), 3.16 (dd, 9.0, 8.0, H-2), 3.40 (t-like, 9.0, H-3), 3.28 (H-4, 4), 3.49
3.53 (m, H-5), 3.77 (dd, 11.8, 6.6, H-6), 4.18 (dd, 11.8, 1.5, H-6), 4.46 (d, 7.5, H-1), 3.33 (H-3, 5), 3.87 (dd, 11.9,
2.1, H-6), 3.66 (dd, 11.9, 5.5, H-6); 13C-NMR (100 MHz, CD3OD): 95.9 (C-1), 154.1 (C-3), 110.4 (C-4), 43.0 (C-5),
76.6 (C-6), 48.1 (C-7), 90.2 (C-8), 50.1 (C-9), 22.9 (C-10), 169.6 (C-11), 52.3 (OMe), 22.7, 173.4 (Ac), 100.3 (C-1),
75.1 (C-2), 78.3 (C-3), 72.2 (C-4), 78.1 (C-5), 70.5 (C-6), 105.4 (C-1), 75.8 (C-2), 78.3 (C-3), 72.2 (C-4), 78.4
(C-5), 63.3 (C-6). Lamiophlomis rotata (Labiatae).50)
6-O-a -D-Galactopyranosylbarlerin
1639, 1439, 1377, 1292, 1188, 1086, 1024, 866, 615; 1H-NMR (400 MHz, CD3OD): 5.95 (d, 2.0, H-1), 7.43 (d, 1.1, H3), 3.07 (br d, 8.8, H-5), 4.34 (m, H-6), 2.17 (br d, 15.0, H-7), 1.95 (dd, 15.0, 5.5, H-7), 2.99 (dd, 8.8, 2.0, H-9), 1.50 (s,
H3-10), 3.71 (s, OMe), 2.01 (s, Ac), 4.63 (d, 7.7, H-1), 3.17 (dd, 9.0, 7.7, H-2), 3.36 (t-like, 9.0, H-3), 3.28 (t-like, 9.0,
H-4), 3.543.58 (m, H-5), 3.89 ( H-6), 3.79 (H-6), 4.91 (d, 3.5, H-1), 3.76 (H-2), 3.82 (H-3), 3.93 (H-4), 3.98 (H5), 3.73 (H2-6); 13C-NMR (100 MHz, CD3OD): 95.8 (C-1), 154.1 (C-3), 110.4 (C-4), 43.0 (C-5), 76.3 (C-6), 48.3 (C7), 89.9 (C-8), 50.1 (C-9), 22.9 (C-10), 169.4 (C-11), 52.3 (OMe), 22.7, 173.1 (Ac), 100.2 (C-1), 75.1 (C-2), 78.7 (C3), 72.3 (C-4), 77.2 (C-5), 68.4 (C-6), 100.7 (C-1), 71.0 (C-2), 72.1 (C-3), 71.7 (C-4), 72.8 (C-5), 63.4 (C-6).
Lamiophlomis rotata (Labiatae).50)
6-epi-Barlerin
C19H28O12: 448.1580; amorphous powder; 1H-NMR (400 MHz, CD3OD): 5.90 (d, 2.0, H-1), 7.40 (br s, H-3), 4.38 (dt,
4.5, 1.0, H-6), 1.48 (s, H3-10), 3.67 (s, OMe), 4.64 (d, 8.0, H-1), 3.66 (br d, 12.0, H-6), 3.89 (br d, 12.0, H-6), other
protons (not assigned); 13C-NMR (100 MHz, CD3OD): 93.1 (C-1), 152.9 (C-3), 108.0 (C-4), 42.2 (C-5), 76.7 (C-6), 47.5
(C-7), 86.4 (C-8), 48.5 (C-9), 20.5 (C-10), 169.3 (C-11), 51.5 (OMe), 98.2 (C-1), 72.8 (C-2), 76.2 (C-3), 69.9 (C-4),
76.6 (C-5), 60.8 (C-6). Mussaenda macrophylla (Rubiaceae).51)
6-O-a -D-Galactopyranosylshanzhiside methyl ester

C23H36O16: 568.2003; amorphous soild; [a ]D20 29.0 (c0.14, H2O); UV: 237, 203; IR (KBr): 3408, 2929, 1691, 1641,
1439, 1383, 1309, 1084, 1057, 1020, 868, 579; 1H-NMR (400 MHz, CD3OD): 5.49 (d, 2.9, H-1), 7.39 (d, 1.0, H-3), 3.00
(dd, 10.0, 3.0, H-5), 4.03 (m, H-6), 1.98 (dd, 13.3, 6.4, H-7), 1.81 (dd, 13.3, 5.8, H-7), 2.60 (dd, 10.0, 2.9, H-9), 1.25 (s,
H3-10), 3.72 (s, OMe), 4.64 (d, 8.0, H-1), 3.18 (dd, 8.8, 8.0, H-2), 3.37 (t-like, 8.8, H-3), 3.34 (H-4 ), 3.503.55 (m,
H-5), 3.89 (H-6, 5), 3.79 (H-6), 4.87 (d, 2.8, H-1), 3.75 (H-2, 3), 3.91 (H-4), 3.69 (H-6); 13C-NMR (100 MHz,
CD3OD): 95.5 (C-1), 153.1 (C-3), 111.8 (C-4), 41.9 (C-5), 77.8 (C-6), 49.5 (C-7), 79.4 (C-8), 52.1 (C-9), 25.0 (C-10),
170.0 (C-11), 52.2 (OMe), 100.3 (C-1), 74.9 (C-2), 78.4 (C-3), 72.1 (C-4), 77.0 (C-5), 68.3 (C-6), 100.5 (C-1),
70.7 (C-2), 71.9 (C-3), 71.3 (C-4), 72.7 (C-5), 63.0 (C-6). Lamiophlomis rotata (Labiatae).50)
5-Dehydro-8-epi-mussaenoside
C17H24O10: 388.1369; isolated as tetraacetate; amorphous powder; UV (MeOH): 280.6 (3.81), 235 (4.04); IR (KBr):
3475, 1751, 1640; 1H-NMR (400 MHz, CDCl3): 4.93 (d, 9.5, H-1), 7.43 (d, 1.0, H-3), 5.84 (br s, H-6), 1.95 (d, 18.0, H7), 2.64 (d, 18.0, H-7), 3.42 (dd, 9.5, 3.0, H-9), 1.31 (s, H3-10), 3.74 (s, OMe), 4.82 (d, 8.0, H-1), 4.98 (dd, 8.5, 8.0, H2), 5.23 (dd, 9.5, 8.5, H-3), 5.09 (dd, 8.5, 9.0, H-4), 3.75 (ddd, 9.5, 4.5, 2.5, H-5), 4.13 (dd, 12.5, 2.5, H-6), 4.33 (dd,
12.5, 4.5 H-6), 1.95, 2.01, 2.03, 2.40 (each s, 4Ac); 13C-NMR (100 MHz, CDCl3): 93.0 (C-1), 153.3 (C-3), 111.1 (C4), 137.1 (C-5), 132.2 (C-6), 38.3 (C-7), 78.3 (C-8), 46.2 (C-9), 24.7 (C-10), 168.6 (C-11), 52.5 (OMe), 96.3 (C-1), 70.6
(C-2), 72.5 (C-3), 68.6 (C-4), 74.3 (C-5), 61.8 (C-6), 20.5, 20.6, 20.7, 20.8, 169.1, 169.4, 170.1, 170.6 (4Ac).
Wendlandia tinctoria (Rubiaceae).35)
August 2009
111.
112.
113.
781
Eriobioside (Ipolamiide 6-O-b -glucopyranoside)

CD3OD): 5.80 (s, H-1), 7.43 (s, H-3), 2.26 (ddd, 13.5, 8.2, 5.2, H-6), 2.09 (ddd, 14.3, 9.5, 7.9, H-6), 1.97 (dd, 12.2, 8.6,
H-7), 1.56 (ddd, 12.2, 6.9, 5.2, H-7), 2.50 (s, H-9), 1.15 (s, H3-10), 3.73 (s, OMe), 4.61 (d, 7.9, H-1), 3.19 (t, 8.0, H-2),
3.38 (overlapped, H-3), 3.31 (overlapped, H-4), 3.51 (overlapped, H-5), 4.20 (dd, 11.8, 1.8, H-6), 3.80 (dd, 11.8, 6.2,
H-6), 4.42 (d, 7.8, H-1), 3.21 (t, 8.0, H-2), 3.36 (overlapped, H-3), 3.31 (overlapped, H-4), 3.28 (overlapped, H-5 ),
3.88 (d, 11.8, H-6), 3.67 (dd, 11.8, 4.1, H-6); 13C-NMR (100 MHz, CD3OD): 94.5 (C-1), 152.7 (C-3), 115.3 (C-4), 71.7
(C-5), 38.9 (C-6), 40.5 (C-7), 79.0 (C-8), 61.8 (C-9), 23.4 (C-10), 168.1 (C-11), 51.7 (OMe), 99.7 (C-1), 74.4 (C-2),
77.9 (C-3), 71.8 (C-4), 77.4 (C-5), 69.9 (C-6), 105.1 (C-1), 74.4 (C-2), 77.5 (C-3), 71.9 (C-4), 78.0 (C-5), 62.8
(C-6). Lamium eriocephalum ssp. eriocephalum (Lamiaceae).52)
Lamerioside
CD3OD): 5.83 (s, H-1), 7.43 (s, H-3), 2.54 (dd, 14.8, 8.2, H-6), 1.81 (dd, 14.8, 11.2, H-6), 4.18 (dd, 11.1, 8.2, H-7), 2.50 (s,
H-9), 1.03 (s, H3-10), 3.75 (s, OMe), 4.61 (d, 7.9, H-1), 3.19 (t, 9.1, H-2), 3.38 (t, 8.9, H-3), 3.33 (t, 8.9, H-4), 3.36 (ddd,
8.9, 5.8, 2.0, H-5), 3.90 (dd, 11.9, 2.0, H-6), 3.67 (dd, 11.9, 5.8, H-6); 13C-NMR (100 MHz, CD3OD): 93.5 (C-1), 152.1 (C3), 116.0 (C-4), 66.3 (C-5), 47.0 (C-6), 78.4 (C-7), 79.8 (C-8), 59.0 (C-9), 15.9 (C-10), 168.0 (C-11), 51.7 (OMe), 99.6 (C1), 74.5 (C-2), 77.5 (C-3), 71.8 (C-4), 77.9 (C-5), 62.9 (C-6). Lamium eriocephalum ssp. eriocephalum (Lamiaceae).52)
Tudoside
C18H23O13: 450.1373; viscous oil; [a ]D20 172.5 (c0.030, MeOH); 1H-NMR (400 MHz, acetone-d6): 5.73 (s, H-1), 7.31 (d,
1.9, H-3), 3.30 (m, H-5), 3.39 (d, 3.0, H-6), 3.95 (d, 2.6, H-7), 2.43 (dd, 8.2, 1.3, H-9), 9.59 (s, H-10), 3.71 (s, OMe), 4.58 (d,
7.7, H-1), 3.15 (dd, 8.0, 8.0, H-2), 3.34 (dd, 8.0, 8.0, H-4), 3.59 (m, H-5), 3.85 (dd, 12.1, 2.0, H-6), 3.59 (m, H-6); 13CNMR (100 MHz, CD3OD): (exists as hemiacetal mixture in CD3OD) 94.6 (C-1), 154.7 (C-3), 107.4 (C-4), 33.7 (C-5), 60.8
(C-6), 58.7 (C-7), 82.1 (C-8), 46.8 (C-9), 98.4 (C-10), 168.7 (C-11), 100.1 (C-1), 74.6 (C-2), 77.9 (C-3), 71.6 (C-4), 78.3
(C-5), 62.8 (C-6), 51.8 (OMe), 54.2 (OCD3). Pentas lanceolata (Rubiaceae).53)
114.
6b -Hydroxy-7-epigardoside methyl ester

C17H24O11: 404.1318; amorphous powder; [a ]D28 17.5 (c0.032, MeOH); UV (MeOH): 236 (3.01); IR (KBr); 3400, 2925,
1692, 1638, 1235, 1156, 947, 840; 1H-NMR (500 MHz, DMSO-d6): 5.61 (d, 2.0, H-1), 7.34 (d, 1.0, H-3), 2.81 (br d, 8.0, H-5),
4.08 (br s, H-6), 4.02 (br s, H-7), 3.123.15 (m, H-9), 5.21 (d, 2.5, H2-10) , 3.64 (s, MeO), 4.41 (d, 8.5, H-1), 2.94 (t, 8.5, H2), 3.123.15 (m, H-3), 3.03 (t, 8.5, H-4), 3.133.16 (m, H-5), 3.44 (dd, 11.5, 6.0, H-6), 3.68 (dd, 11.5, 5.0, H-6); 13CNMR (125 MHz, DMSO-d6): 95.0 (C-1), 152.2 (C-3), 107.9 (C-4), 35.5 (C-5), 73.7 (C-6), 73.5 (C-7), 150.4 (C-8), 41.8 (C-9)
110.0 (C-10), 166.3 (C-11), 50.9 (OMe), 98.4 (C-1), 72.9 (C-2), 76.6 (C-3), 70.0 (C-4), 77.2 (C-5), 61.0 (C-6). Alibertia
edulis (Rubiaceae).54)
Group 3b (Iridoid glycosides with 10-carbon skeleton, valeriana type)

Viburtinoside A (7-O-Acetylviburtinoside II)
C34H44O16: 708.2629; creamy white amorphous powder; [a ]D 59.0 (c0.26, MeOH); UV (MeOH): 309
(4.00), 297 (3.90), 225 (3.70); IR (KBr): 3405, 1733, 1700, 1630, 1600, 1515, 1240, 830; 1H-NMR
(300 MHz, acetone-d6): 6.17 (d, 5.4, H-1), 6.37 (br s, H-3), 2.95 (br q, H-5), 2.06 (m, H-6), 5.07 (t like, 3.6,
H-7), 2.42 (dd, 9.9, 5.4, H-9), 4.16 (br d, 11.3, H2-10), 4.07 (dd, 12.5, 1.3, H2-11), 2.23 (d, 7.0, H2-2), 2.10
(m, H-3), 0.95 (d, 6.0, H3-4, 5), 4.62 (d, 8.1, H-1), 4.87 (dd, 9.3, 8.1, H-2), 3.53 (t-like, 9.3, H-3), 3.42
3.29 (m, H-4, 5), 3.85 (br d, 12.9, H-6), 3.70 (br dd, 12.5, 5.1, H-6), 7.55 (d, 8.7, H-2, 6), 6.90 (d, 8.7,
H-3, 5), 7.63 (d, 15.9, H-7), 6.40 (d, 15.9, H-8), 1.95, 1.89 (each s, 2Ac); 13C-NMR (75 MHz, acetoned6): 90.3 (C-1), 139.8 (C-3), 115.4 (C-4), 32.7 (C-5), 35.6 (C-6), 80.3 (C-7), 81.6 (C-8), 45.1 (C-9), 67.2 (C10), 68.7 (C-11), 171.2 (C-1), 43.6 (C-2), 26.0 (C-3), 22.4 (C-4, 5), 100.5 (C-1), 74.7 (C-2), 76.0 (C3), 71.8 (C-4), 77.2 (C-5), 62.8 (C-6), 126.8 (C-1), 130.8 (C-2, 6), 116.5 (C-3, 5), 160.4 (C-4),
145.5 (C-7), 115.6 (C-8), 166.4 (C-9), 20.6, 20.5, 170.7, 170.1 (2Ac). Viburnum tinus (Adoxaceae).55)
116. Viburtinoside B
C34H44O16: 708.2629; creamy-white amorphous powder; [a ]D 61.0 (c0.23, MeOH); UV (MeOH):
311 (4.10), 299 (3.90), 226 (3.70); IR (KBr): 3400, 1735, 1705, 1625, 1600, 1510, 1235, 835; 1H-NMR
(300 MHz, acetone-d6): 6.15 (d, 5.4, H-1), 6.35 (br s, H-3), 2.92 (br q, H-5), 2.03 (m, H-6), 5.01 (t-like,
3.6, H-7), 2.35 (dd, 9.9, 5.4, H-9), 4.14 (br d, 11.5, H2-10), 4.07 (dd, 12.5, 1.2, H2-11), 2.19 (d, 7.0, H2), 2.12 (m, H-3), 0.93 (d, 6.0, H3-4, 5), 4.56 (d, 8.1, H-1), 4.85 (dd, 9.3, 8.1, H-2), 3.50 (t-like,
9.1, H-3), 3.403.27 (m, H-4, 5), 3.83 (br d,12.5, H-6), 3.69 (br dd, 12.5, 5.1, H-6), 7.76 (d, 8.7, H2, 6), 6.82 (d, 8.7, H-3, 5), 6.88 (d, 12.9, H-7), 5.78 (d, 12.9, H-8), 1.98, 1.95 (each s, 2Ac);
13
C-NMR (75 MHz, acetone-d6): 90.3 (C-1), 139.7 (C-3), 115.3 (C-4), 32.9 (C-5), 35.8 (C-6), 80.2 (C7), 81.6 (C-8), 45.1 (C-9), 67.2 (C-10), 68.7 (C-11), 171.3 (C-1), 43.6 (C-2), 26.0 (C-3), 22.4 (C-4,
5), 100.5 (C-1),74.7 (C-2), 75.9 (C-3), 71.8 (C-4), 77.2 (C-5), 62.8 (C-6), 126.9 (C-1), 133.6 (C2, 6), 115.2 (C-3, 5), 159.6 (C-4), 144.2 (C-7), 114.7 (C-8), 166.4 (C-9), 20.5, 20.2, 170.2,
170.1 (2Ac). Viburnum tinus (Adoxaceae).55)
117. 10-Isovalerylkanokoside C
C32H60O18: 722.2996; amorphous; [a ]D26 68.5 (c0.5, MeOH); UV (MeOH): 208.0; IR (film):
3421, 2959, 1738, 1675, 1635, 1372; 1H-NMR (500 MHz, CD3OD): 6.53 (s, H-1), 6.47 (d, 1.8, H3), 3.13 (d, 7.8, H-5), 4.11 (d, 2.4, H-6), 3.37 (m, H-7), 2.14 (d, 7.8, H-9), 4.33 (d, 11.4, Ha-10), 4.27
(d, 11.4, Hb-10), 4.37 (d, 12.0, Ha-11), 4.26 (d,12.0, Hb-11), 4.42 (d, 7.8, H-1), 3.26 (dd, 9.0, 7.8, H2), 3.31 (m, H-3), 3.34 (m, H-4), 3.50 (m, H-5), 3.81 (m, Ha-6), 4.19 (dd, 11.4, 6.6, Hb-6),
2.21 (dd, 7.2, 2.4, H-2), 2.07 (m, H-3), 0.97 (d, 6.6, H3-4, 5), 2.31 (d, 7.2, H-2), 2.12 (m, H-3),
0.99 (d, 6.6, H3-4,5), 4.40 (d, 7.8, H-1), 3.26 (dd, 9.0, 7.8, H-2), 3.39 (m, H-3), 3.37 (m, H4),3.40 (m, H-5), 3.71 (dd, 12.0, 5.4, Ha-6), 3.90 (dd, 12.0, 6.0, Hb-6); 13C-NMR (125 MHz,
CD3OD): 90.1 (C-1), 142.8 (C-3), 108.8 (C-4), 35.4 (C-5), 59.8 (C-6), 60.3 (C-7), 78.4 (C-8), 43.9
(C-9), 69.4 (C-10), 69.5 (C-11), 172.8 (C-1), 44.0 (C-2), 26.7 (C-3), 22.6 (C-4, 4), 22.7 (C-5,
5), 174.5 (C-1), 44.0 (C-2), 26.8 (C-3), 101.9 (C-1), 75.0 (C-2), 77.9 (C-3), 71.6 (C-4), 77.0
(C-5), 70.0 (C-6), 105.0 (C-1), 75.1 (C-2), 78.0 (C-3), 71.7 (C-4), 78.0 (C-5), 62.7 (C6). Valeriana fauriei (Valerianaceae).22)
115.
782
Vol. 57, No. 8

Group 3c (Iridoid glycosides with 10-carbon skeleton, plumeria type)
118.
13(R)-epi-Gaertneroside
C26H28O13: 548.1529; viscous oil; [a ]D20 153.1 (c0.095, MeOH); 1H-NMR (400 MHz, CD3OD): 5.34 (d, 3.7, H-1),
7.47 (d, 1.5, H-3), 3.88 (m, H-5), 6.45 (dd, 5.8, 2.6, H-6), 5.46 (dd, 5.5, 1.8, H-7), 2.99 (dd, 8.1, 3.6, H-9), 7.24 (d, 1.5, H10), 5.39 (d, 1.1, H-13), 4.64 (d, 8.0, H-1), 3.21 (dd, 9.2, 8.0, H-2), 3.34 (m, H-3), 3.27 (m, H-4), 3.63 (H-6), 3.73 (s,
OMe), 7.20 (d, 8.4, H-2, 6), 6.76 (d, 8.8, H-3, 5); 13C-NMR (100 MHz, CD3OD): 93.8 (C-1), 152.2 (C-3), 111.4 (C-4),
39.9 (C-5), 141.0 (C-6), 130.2 (C-7), 97.9 (C-8), 50.6 (C-9), 150.6 (C-10), 137.9 (C-11), 172.5 (C-12), 69.5 (C-13), 168.4
(C-14), 99.8 (C-1), 74.5 (C-2), 77.8 (C-3), 71.4 (C-4), 78.5 (C-5), 62.6 (C-6), 51.9 (OMe), 133.3 (C-1), 129.2 (C2, 6), 116.2 (C-3, 5), 158.4 (C-4). Pentas lanceolata (Rubiaceae).53)
119.
13(R)-epi-Epoxygaertneroside
C26H28O14: 564.1478; viscous oil; [a ]D20 228.8 (c0.032, MeOH); 1H-NMR (400 MHz, CD3OD): 5.33 (d, 1.4, H-1),
7.55 (d, 1.6, H-3), 3.45 (d, 8.1, H-5), 3.42 (m, H-6), 4.02 (d, 2.4, H-7), 2.77 (dd, 8.4, 1.1, H-9), 7.03 (d, 1.6, H-10), 5.39
(d, 1.4, H-13), 4.53 (d, 7.8, H-1), 3.12 (dd, 8.9, 8.0, H-2), 3.35 (m, H-3), 3.30 (m, H-4), 3.21 (m, H-5), 3.85 (dd, 12.0,
2.0, H-6), 3.70 (m, H-6), 7.21 (d, 8.3, H-2, 6), 6.76 (d, 8.6, H-3, 5), 3.76 (s, OMe); 13C-NMR (100 MHz, CD3OD):
92.8 (C-1), 153.9 (C-3), 108.0 (C-4), 33.0 (C-5), 59.2 (C-6), 57.8 (C-7), 92.6 (C-8), 43.6 (C-9), 148.1 (C-10), 140.5 (C11), 171.7 (C-12), 69.6 (C-13), 168.0 (C-14), 51.9 (OMe), 99.6 (C-1), 74.4 (C-2), 77.8 (C-3), 71.3 (C-4), 78.4 (C-5),
62.5 (C-6), 132.4 (C-1), 129.3 (C-2, 6), 116.3 (C-3, 5), 158.6 (C-4). Pentas lanceolata (Rubiaceae).53)
120.
(E)-Uenfoside
C26H28O13: 548.1529; viscous oil (isolated as mixture with Z-isomer); [a ]D20 185.4 (c0.034, MeOH); 1H-NMR
(400 MHz, CD3OD): 5.20 (d, 6.2, H-1), 7.46 (d, 1.9, H-3), 3.90 (m, H-5), 6.09 (dd, 5.8, 2.5, H-6), 6.45 (dd, 5.8, 2.3, H-7),
2.55 (dd, 7.0, 6.2, H-9), 5.57 (d, 1.1, H-10), 7.59 (s, H-13), 4.61 (d, 8.1, H-1), 2.71 (dd, 8.9, 8.0, H-2), 3.34 (m, H-3),
3.30 (m, H-4, 5), 3.85 (m, H-6), 3.70 (m, H-6), 7.65 (d, 8.6, H-2, 6), 6.84 (d, 8.9, H-3, 5), 3.74 (s, OMe); 13C-NMR
69.5 (C-10), 124.0 (C-11), 173.6 (C-12), 143.9 (C-13), 168.6 (C-14), 99.7 (C-1), 74.2 (C-2), 77.7 (C-3), 71.3 (C-4),
78.5 (C-5), 62.6 (C-6), 125.6 (C-1), 134.9 (C-2, 6), 117.9 (C-3, 5), 164.1 (C-4), 52.0 (OMe). Pentas lanceolata
(Rubiaceae).53)
121.
(Z)-Uenfoside
C26H28O13: 548.1529; viscous oil (isolated as mixture with E-isomer); 1H-NMR (400 MHz, CD3OD): 5.45 (d, 5.6,
H-1), 7.49 (d, 1.6, H-3), 3.85 (m, H-5), 5.87 (dd, 5.6, 2.4, H-6), 6.38 (dd, 5.8, 2.3, H-7), 2.77 (dd, 7.4, 5.8, H-9), 5.29
(d, 1.9, H-10), 7.06 (d, 1.9, H-13), 4.74 (d, 7.8, H-1), 3.14 (dd, 9.6, 8.2, H-2), 3.30 (H-3-5), 3.85 ( H-6), 3.70 (
H-6), 7.97 (d, 8.9, H-2, 6), 6.78 (d, 8.9, H-3, 5), 3.73 (s, OMe); 13C-NMR (100 MHz,CD3OD): 94.8 (C-1), 152.8
(C-3), 110.4 (C-4), 40.5 (C-5), 129.9 (C-6), 141.3 (C-7), 99.0 (C-8), 49.9 (C-9), 73.4 (C-10), 124.9 (C-11), 169.3
(C-12), 143.3 (C-13), 169.3 (C-14), 52.0 (OMe), 100.3 (C-1), 74.6 (C-2), 77.8 (C-3), 71.4 (C-4), 78.4 (C-5),
62.5 (C-6), 126.6 (C-1), 135.0 (C-2, 6), 116.4 (C-3, 5), 161.8 (C-4). Pentas lanceolata (Rubiaceae).53)
122.
Daphmacropodosidine A
C40H57NO13: 759.3829; colorless crystals; mp 176178 C; [a ]D29.3 43.5 (c0.84, MeOH); UV (MeOH):
374.4 (2.42), 307.2 (2.73); IR (KBr): 3422, 2930, 1729, 1643, 1549, 1458, 1400, 1158, 1082, 1042; 1H-NMR
(500 MHz, CD3OD): unit a: 5.05 (d, 7.5, H-1), 7.22 (s, H-3), 3.21 (m, H-5), 2.83 (m, H-6), 2.06 (m, H-6), 5.76
(s, H-7), 2.63 (m, H-9), 4.27 (d, 13.2, H-10), 4.16 (d, 13.2, H-10), 4.77 (d, 7.6, H-1), 3.35 (m, H-2), 4.95 (t,
7.0, H-3), 3.46 (m, H-4), 3.32 (m, H-5), 3.84 (d, 12.0, H-6), 3.66 (dd, 12.0, 5.1, H-6); unit b: 2.55 (d, 10.8,
H-1), 2.43 (d, 10.8, H-1), 1.73 (m, H-3), 1.35 (m, H-3), 1.96 (m, H-4), 1.58 (m, H-4), 2.31 (m, H-6), 2.90 (d,
12.4, H-7), 2.77 (overlapped, H-7), 2.11 (m, H-11), 1.65 (m, H-11), 2.45 (m, H-12), 2.27 (m, H-12), 2.76 (m,
H-13), 1.68 (m, H-13), 3.00 (m, H-14), 3.55 (m, H-15), 1.83 (m, H-16), 1.73 (m, H-16), 2.57 (m, H-17), 2.33
(m, H-17), 2.04 (m, H-18), 0.84 (d, 6.9, H3-19), 0.93 (d, 6.7, H3-20), 4.06 (d, 12.4, H-21), 3.88 (d, 12.4, H-21),
3.17 (s, OMe), 2.34 (s, NMe); 13C-NMR (125 MHz, CD3OD): unit a: 97.8 (C-1), 148.7 (C-3), 118.5 (C- 4),
37.7 (C-5), 40.0 (C-6), 128.4 (C-7), 145.0 (C-8), 47.5 (C-9), 61.6 (C-10), 175.7 (C-11), 100.2 (C-1), 73.2 (C2), 78.4 (C-3), 69.7 (C-4), 78.3 (C-5), 62.2 (C-6); unit b: 61.2 (C-1), 102.3 (C-2), 22.8 (C- 3), 23.2 (C-4),
37.7 (C-5), 34.1 (C-6), 56.7 (C-7), 47.3 (C-8), 146.5 (C-9), 135.4 (C-10), 27.8 (C-11, 12), 40.5 (C-13), 44.2
(C-14), 56.0 (C-15), 29.0 (C-16), 43.6 (C-17), 32.5 (C-18), 16.7 (C-19), 17.7 (C-20), 64.3 (C-21), 175.9 (C22), 47.2 (OMe), 46.8 (NMe). Daphniphyllum macropodum (Daphniphyllaceae).56)
August 2009
123.
783
Daphmacropodosidine B
C39H53NO12: 727.3567; white amorphous powder; [a ]D29.3 0 (c0.26, MeOH); UV (MeOH): 377.8 (2.26),
308.6 (2.52); IR (KBr): 3425, 2927, 1735, 1641, 1549, 1452, 1397, 1169, 1146, 1086, 1044; 1H-NMR
(500 MHz, C5D5N): unit a: 5.68 (d, 7.3, H-1), 7.94 (s, H-3), 3.57 (m, H-5), 3.15 (m, H-6), 2.44 (m, H-6), 6.02
(s, H-7), 3.13 (m, H-9), 4.77 (d, 14.2, H-10), 4.65 (d, 14.2, H-10), 5.39 (d, 7.8, H-1), 4.06 (m, H-2), 4.25 (t,
8.9, H-3), 3.99 (t, 8.9, H-4), 4.09 (m, H-4), 5.01 (d, 11.3, H-6), 4.55 (dd, 11.3, 6.7, H-6); unit b: 2.32 (d,
10.4, H-1), 2.01 (d, 10.4, H-1), 4.45 (br d, 4.2, H2-3), 2.26 (dd, 16.8, 4.2, H-4), 1.88 (d, 16.8, H-4), 2.09 (m, H6), 2.63 (d, 11.6, H-7), 2.46 (m, H-7), 2.64 (m, H-11), 2.40 (m, H-11), 1.97 (m, H-12), 1.62 (m, H-12), 2.47 (m,
H-13), 1.54 (m, H-13), 2.95 (m, H-14), 3.53 (m, H-15), 1.96 (m, H-16), 1.56 (m, H-16), 2.48 (m, H-17), 2.36
(m, H-17), 2.33 (m, H-18), 1.08 (d, 6.8, H3-19, 20), 4.72 (d, 11.6, H-21), 4.38 (d, 11.6, H-21), 2.11 (s, NMe);
13
C-NMR (125 MHz, C5D5N): unit a: 97.7 (C-1), 151.9 (C-3), 113.2 (C- 4), 36.2 (C-5), 39.6 (C-6), 127.2 (C-7),
145.6 (C-8), 47.0 (C-9), 61.0 (C-10), 169.8 (C-11), 100.7 (C-1), 74.9 (C-2), 78.2 (C-3), 71.6 (C-4), 75.8 (C5), 64.6 (C-6); unit b: 64.4 (C-1), 159.6 (C-2), 91.2 (C- 3), 27.6 (C-4), 37.2 (C-5), 34.8 (C-6), 55.5 (C-7), 46.8
(C-8), 147.3 (C-9), 133.5 (C-10), 27.6 (C-11), 27.7 (C-12), 40.0 (C-13), 49.9 (C-14), 55.5 (C-15), 28.9 (C-16),
43.0 (C-17), 32.6 (C-18), 20.7 (C-19), 20.8 (C-20), 70.1 (C-21), 175.3 (C-22), 46.6 (NMe). Daphniphyllum
macropodum (Daphniphyllaceae).56)
124.
125.
126.
Group 3d (Rearranged iridoid glycosides: with 10-carbon skeleton)

2-O-(3-Hydroxybenzoyl)-8-epikingiside
C24H28O13: 524.1529; white amorphous powder; [a ]D26 67.4 (c0.7, MeOH); IR (KBr): 3429, 1716,
1636, 1453, 1287, 1104, 981, 754; 1H-NMR (400 MHz, CD3OD): 5.54 (d, 5.0, H-1), 7.25 (d, 1.2, H-3),
2.97 (br q, 6.9, H-5), 2.57 (dd, 16.9, 8.4, H-6), 2.83 (dd, 16.9, 6.3, H-6), 4.36 (dq, 8.2, 6.4, H-8), 2.09 (td,
7.9, 5.0, H-9), 1.46 (d, 6.4, H3-10), 3.45 (s, OMe), 4.98 (d, 8.1, H-1), 4.95 (dd, 8.1, 9.2, H-2), 3.70 (dd,
9.2, 8.7, H-3), 3.41 (dd, 8.7, 9.0, H-4), 3.47 (m, H-5), 3.97 (dd, 12.0, 1.9, H-6), 3.72 (dd, 12.0, 4.5, H6), 7.39 (t, 2.4, H-2), 7.03 (dd, 7.9, 2.4, H-4), 7.27 (t, 7.9, H-5), 7.48 (dd, 7.9, 2.4, H-6); 13C-NMR
(100 MHz, CD3OD): 95.4 (C-1), 153.2 (C-3), 110.6 (C-4), 26.5 (C-5), 33.8 (C-6), 174.4 (C-7), 75.8 (C8), 42.4 (C-9), 20.8 (C-10), 167.7 (C-11), 51.8 (OMe), 98.3 (C-1), 75.1 (C-2), 75.8 (C-3), 71.8 (C-4),
78.7 (C-5), 62.7 (C-6), 134.4 (C-1), 117.4 (C-2), 158.6 (C-3), 121.3 (C-4), 130.5 (C-5), 121.9 (C6), 167.1 (C-7). Gentiana rhodantha (Gentianaceae).49)
2-O-(3-Hydroxybenzoyl)-kingiside
C24H28O13: 524.1529; white amorphous powder; [a ]D26 86.6 (c0.7,MeOH); IR (KBr): 3427, 1719,
1640, 1288, 1076; 1H-NMR (400 MHz, CD3OD): 5.70 (d, 2.9, H-1), 7.22 (s, H-3), 3.15 (dt, 8.5, 4.9, H5), 2.73 (dd, 16.0, 4.5, H-6), 2.89 (dd, 16.0, 5.6, H-6), 4.70 (dq, 6.4, 6.4, H-8), 2.55 (ddd, 8.5, 6.4, 2.9, H9), 1.46 (d, 6.7, H3-10), 3.34 (s, OMe), 5.00 (d, 8.0, H-1), 4.96 (dd, 8.0, 8.9, H-2), 3.74 (t, 8.9, H-3),
3.47 (dd, 8.7, 8.0, H-4), 3.48 (m, H-5), 3.99 (dd, 12.6, 1.0, H-6), 3.75 (dd, 12.6, 5.4, H-6), 7.42 (d,
2.0, H-2), 7.07 (dd, 8.0, 2.0, H-4), 7.31 (t, 8.0, H-5), 7.49 (dd, 8.0, 2.0, H-6); 13C-NMR (100 MHz,
CD3OD): 93.8 (C-1), 153.7 (C-3), 111.6 (C-4), 26.4 (C-5), 33.7 (C-6), 175.0 (C-7), 75.6 (C-8), 39.8 (C9), 17.2 (C-10), 167.2 (C-11), 51.7 (OMe), 97.4 (C-1), 75.0 (C-2), 75.2 (C-3), 71.6 (C-4), 78.3 (C5), 62.6 (C-6), 132.2 (C-1), 117.2 (C-2), 158.5 (C-3), 121.3 (C-4), 130.5 (C-5), 121.8 (C-6 ),
166.8 (C-7). Gentiana rhodantha (Gentianaceae).49)
6-O-p-Coumaroyl-8-epikingiside
C26H30O13: 550.1686; yellow amorphous powder; [a ]D26 34.3 (c1.8, MeOH); IR (KBr): 3421, 1707, 1604,
1514, 1441, 1279, 1167, 1077; 1H-NMR (400 MHz, CD3OD): 5.29 (d, 7.9, H-1), 7.51 (s, H-3), 2.98 (m, H-5),
2.29 (dd, 16.4, 8.5, H-6), 2.78 (dd, 16.4, 5.4, H-6), 4.34 (br q, 6.3, H-8), 2.07 (br q, 7.4, H-9), 1.41 (d, 6.3, H310), 3.67 (s, OMe), 4.73 (d, 8.0, H-1), 3.25 (dd, 8.7, 8.0, H-2), 3.42 (dd, 8.7, 6.6, H-3), 3.31 (m, H-4), 3.56
(m, H-5), 4.35 (dd, 12.0, 5.7, H-6), 4.58 (dd, 12.0, 2.1, H-6), 7.45 (d, 8.5, H-2, 6), 6.80 (d, 8.5, H-3, 5),
7.59 (d, 16.0, H-7), 6.32 (d, 16.0, H-8); 13C-NMR (100 MHz, CD3OD): 96.4 (C-1), 154.4 (C-3), 109.3 (C-4),
28.4 (C-5), 34.7 (C-6), 174.6 (C-7), 75.8 (C-8), 41.7 (C-9), 21.7 (C-10), 168.9 (C-11), 52.0 (OMe), 98.7 (C-1),
74.6 (C-2), 77.6 (C-3), 71.5 (C-4), 75.6 (C-5), 63.6 (C-6), 126.9 (C-1), 131.3 (C-2, 6), 116.8 (C-3, 5),
161.3 (C-4), 147.0 (C-7), 114.8 (C-8), 168.2 (C-9). Gentiana rhodantha (Gentianaceae).49)
Group 4 (Secoiridoid glycosides)
127.
Verbenabraside A
C25H32O12: 524.1893; amorphous powder; [a ]D13 86.1 (c2.1, MeOH); 1H-NMR (500 MHz, CD3OD): 3.80
(dd, 11.0, 2.0, Ha-1), 3.57 (ca. Hb-1), 4.18 (dd, 9.5, 3.5, Ha-3), 3.91 (dd, 9.5, 4.5, Hb-3), 3.02 (m, H-4), 3.24 (m,
H-5), 5.01 (br dd, 6.5, 6.5, H-6), 2.09 (br dd, 14.0, 5.5, Ha-7), 1.50 (m, Hb-7), 1.75 (ca. H-8), 1.77 (ca. H-9),
1.02 (d, H3-10), 4.36 (d, 7.5, H-1), 3.31 (ca. H-2), 3.58 (ca. H-3), 4.83 (ca. H-4), 3.54 (ca. H-5), 3.63 (ca.
Ha-6), 3.54 (ca. Hb-6), 7.06 (s, H-2), 6.79 (d, 8.0, H-5), 6.96 (d, 8.0, H-6), 7.60 (d, 16.0, H-7), 6.30 (d,
16.0, H-8), 13C-NMR (125 MHz, CD3OD): 61.5 (C-1), 70.8 (C-3), 43.7 (C-4), 46.1 (C-5), 85.4 (C-6), 42.8 (C7), 34.1 (C-8), 52.6 (C-9), 17.7 (C-10), 180.9 (C-11), 104.6 (C-1), 75.2 (C-2), 75.8 (C-3), 72.6 (C-4), 76.3
(C-5), 62.6 (C-6), 127.8 (C-1), 115.4 (C-2), 146.9 (C-3), 149.8 (C-4), 116.7 (C-5), 123.1 (C-6), 147.7
(C-7), 114.9 (C-8), 168.7 (C-9). Verbena brasiliensis (Verbenaceae).57)
128.
Verbenabraside B
C25H32O12: 524.1893; amorphous powder; [a ]D13 39.0 (c4.4, MeOH); 1H-NMR (500 MHz, CD3OD):
3.68 (d, 11.5, Ha-1), 3.61 (d, 11.5, Hb-1), 4.22 (dd, 10.0, 3.5, Ha-3), 3.97 (dd, 10.0, 5.0, Hb-3), 3.03 (ddd,
7.0, 5.0, 3.5, H-4), 3.13 (dd, 7.0, 6.5, H-5), 5.03 (br dd, 7.0, 6.5, H-6), 1.93 (ca. H2-7), 2.01 (m, H-8), 0.95
(d, H3-10), 4.38 (d, 8.0, H-1), 3.31 (dd, 9.5, 8.0, H-2), 3.65 (dd, 9.5, 9.5, H-3), 4.85 (dd, 9.5, 9.5, H-4),
3.53 (ca. H-5), 3.66 (ca. Ha-6), 3.56 (ca. Hb-6), 7.47 (d, 8.5, H-2, 6), 6.82 (d, 8.5, H-3, 5), 7.67 (d,
16.0, H-7), 6.36 (d, 16.0, H-8), 13C-NMR (125 MHz, CD3OD): 65.3 (C-1), 70.3 (C-3), 44.9 (C-4), 54.2
(C-5), 84.6 (C-6), 39.8 (C-7), 37.3 (C-8), 84.3 (C-9), 11.9 (C-10), 180.5 (C-11), 104.5 (C-1), 75.2 (C-2),
75.8 (C-3), 72.6 (C-4), 76.3 (C-5), 62.5 (C-6), 127.2 (C-1),131.3 (C-2, 6), 117.0 (C-3, 5), 147.3 (C7), 114.9 (C-8), 168.6 (C-9). Verbena brasiliensis (Verbenaceae).57)
784
129.
Vol. 57, No. 8

Kankanoside D
C15H26O7: 318.1678; amorphous powder; [a ]D25 30.6 (c0.50, MeOH); IR (KBr): 3410, 2940, 1655, 1078; 1H-NMR
(500 MHz, CD3OD): 4.04 (d, 12.2, H-1), 4.18 (d, 12.2, H-1), 3.56 (ddd, 13.2, 7.4, 2.8, H-3), 3.97 (ddd, 13.2, 8.0, 4.9, H-3),
1.41 (m, H-4), 2.06 (m, H-4), 2.90 (m, H-5), 1.51 (m, Ha -6), 2.01 (m, Hb -6), 2.23 (br dd, ca. 15.0, 8.0, Ha -7), 2.37 (br dd, ca.
15.0, 8.0, Hb -7), 1.69 (s, H3-10), 4.25 (d, 7.7, H-1), 3.16 (dd, 9.2, 7.7, H-2), 3.34 (dd, 9.2, 8.9, H-3), 3.26 (m, H-4), 3.27
(m, H-5), 3.66 (dd, 12.2, 5.2, H-6), 3.86 (dd, 12.2, 1.8, H-6). Cistanche tubulosa (Orobanchaceae).25)
130.
3-O-b -D-Glucopyranosylsweroside
C22H32O14: 520.1791; white amorphous powder; UV (MeOH): 242.6, 206.8; IR (KBr): 3404, 1697, 1616, 1072, 987; 1HNMR (500 MHz, CD3OD) 5.49 (d, 1.5, H-1), 7.53 (s, H-3), 3.053.11 (m, H-5) , 1,611.74 (m, H2-6), 3.83 (ddd, 10.0, 2.5,
1.5, H-7), 4.32 (ddd, 10.0, 9.0, 3.0, H-7), 5.49 (ddd, 20.5, 10.5, 5.5, H-8), 2.65 (br dd, 8.5, 5.5, H-9), 5.25 (d, 20.5, H-10), 5.22
(d, 10.5, H-10), 4.68 (d, 8.0, H-1), 3.193.40 (H-2), 4.384.41 (H-3), 3.193.40 (H-4, 5), 3.513.65 (H2-6), 4.51 (d,
8.0, H-1), 3.193.40 (H-25), 3.513.65 (H2-6); 13C-NMR (125 MHz, CD3OD): 98.1 (C-1), 154.0 (C-3), 105.2 (C-4), 28.5
(C-5), 25.9 (C-6), 69.7 (C-7), 133.3 (C-8), 43.8 (C-9), 120.9 (C-10), 168.5 (C-11), 99.5 (C-1), 74.1 (C-2), 87.3 (C-3), 70.0 (C4), 77.8 (C-5), 62.5 (C-6), 106.0 (C-1), 75.5 (C-2), 78.1 (C-3), 71.6 (C-4), 78.2 (C-5), 62.6 (C-6). Dipsacus asper.58)
131.
6-O-b -Glucopyranosylsecologanoside
C22H32O16: 552.1690; yellow amorphous powder; [a ]D26 86.7 (c1.8, MeOH); IR (KBr): 3425, 1639, 1074; 1H-NMR
(400 MHz, CD3OD): 5.40 (d, 3.2, H-1), 7.20 (s, H-3), 3.24 (m, H-5), 2.14 (m, H-6), 2.85 (m, H-6), 5.73 (dt, 17.0, 9.6,
H-8), 2.84 (m, H-9), 5.26 (dd, 15.0, 3.6, H-10), 5.31 (dd, 9.6, 3.6, H-10), 4.84 (d, 8.0, H-1), 3.26 (m, H-2), 3.61 (m, H3), 3.433.51 (m, H-4, 5), 4.41 (dd, 13.2, 4.8, H-6), 3.84 (dd, 13.2, 2.0, H-6), 4.48 (d, 7.2, H-1), 3.26 (m, H-2),
3.61 (m, H-3), 3.433.51 (m, H-4, 5), 3.88 (dd, 12.5, 5.5, H-6), 3.70 (dd, 12.5, 1.0, H-6); 13C-NMR (100 MHz,
CD3OD): 97.5 (C-1), 152.3 (C-3), 114.8 (C-4), 30.9 (C-5), 38.3 (C-6), 181.3 (C-7), 135.1 (C-8), 45.3 (C-9), 120.3 (C10), 175.3 (C-11), 99.8 (C-1), 74.8 (C-2), 77.7 (C-3), 71.3 (C-4), 77.3 (C-5), 69.8 (C-6), 104.7 (C-1), 74.3 (C-2),
77.6 (C-3), 71.4 (C-4), 77.0 (C-5), 62.4 (C-6). Gentiana rhodantha (Gentianaceae).49)
6-O-b -Glucopyranosylsecologanol
C22H34O15: 538.1897; white amorphous powder; [a ]D26 59.0 (c0.5, MeOH); IR (KBr): 3425, 1639, 1074; 1H-NMR
(400 MHz, CD3OD): 5.39 (d, 4.0, H-1), 7.27 (s, H-3), 3.23 (m, H-5), 1.85 (dt, 14.2, 6.5, H-6), 1.69 (ddd, 14.2, 8.7, 6.5,
H-6), 4.17 (br d, 10.1, H-7), 5.67 (ddd, 17.0, 10.0, 9.5, H-8), 2.24 (ddd, 9.5, 6.8, 4.5, H-9), 5.29 (dd, 9.5, 4.0, H-10), 5.22
(dd, 14.0, 4.0, H-10), 4.79 (d, 7.6, H-1), 3.25 (m, H-2), 3.57 (m, H-3), 3.323.48 (m, H-4, 5), 3.87 (dd, 12.0, 5.0,
H-6), 3.83 (dd, 12.0, 1.0, H-6), 4.50 (d, 7.8, H-1), 3.25 (m, H-2), 3.57 (m, H-3), 3.323.48 (m, H-4, 5), 3.89 (dd,
12.5, 5.5, H-6), 3.70 (dd, 12.5, 1.0, H-6); 13C-NMR (100 MHz, CD3OD): 97.6 (C-1), 150.3 (C-3), 111.8 (C-4), 29.7
(C-5), 33.5 (C-6), 62.2 (C-7), 134.4 (C-8), 45.0 (C-9), 120.8 (C-10), 169.5 (C-11), 99.6 (C-1), 74.6 (C-2), 77.7 (C-3),
71.0 (C-4), 77.3 (C-5), 69.7 (C-6), 104.4 (C-1), 74.0 (C-2), 77.5 (C-3), 70.9 (C-4), 77.1 (C-5), 62.2 (C-6). Gentiana rhodantha (Gentianaceae).49)
Alstonoside
C24H28O13: 524.1529; colorless needles; mp 125126 C; [a ]D25 176.0 (c0.1, MeOH); UV (MeOH): 232 (3.88),
201 (2.45); 1H-NMR (400 MHz, CD3OD): 6.01 (s, H-1), 7.55 (s, H-3), 4.12 (dd, 10.0, 3.7, H-5), 2.56 (dd, 15.3, 10.0, H6), 2.90 (dd, 15.3, 3.7, H-6), 6.25 (br t, 6.5, H-8), 5.11 (dd, 13.2, 6.5, H-10), 4.98 (overlapped, H-10), 4.83 (d, 7.7, H-1),
3.32 (overlapped, H-2, 4), 3.38 (overlapped, H-3), 3.40 (overlapped, H-5), 3.68 (overlapped, H-6), 3.88 (dd, 10.0,
1.5, H-6), 8.02 (dd, 7.2, 1.3, H-2, 6), 7.46 (dd, 7.2, 1.2, H-3, 5), 7.60 (br t, 7.6, H-4), 3.64 (br s, OMe); 13C-NMR
62.6 (C-10), 169.6 (C-11), 100.9 (C-1), 74.6 (C-2), 78.5 (C-3), 71.4 (C-4), 77.9 (C-5), 62.4 (C-6), 134.6 (C-1),
130.5 (C-2, 6), 129.6 (C-3, 5), 134.3 (C-4), 167.8 (C-7), 52.2 (OMe). Alstonia scholaris (Apocynaceae).59)
132.
133.
134.
135.
136.
Group 5 (Iridoid aglycones and derivatives)

5-Deoxy-8-deacetyl-3-O-methyl-6-O-p-hydroxybenzoyl-1,3-di-epi-clandonensine (Compound 1)
C18H24O7: 352.1522; colorless amorphous solid; [a ]D25 110.2 (c0.033, MeOH); IR (KBr): 3550, 3400, 1708,
1656, 1607, 1511, 1260, 960; 1H-NMR (400 MHz, CD3OD): 4.76 (d, 3.9, H-1), 4.80 (dd, 7.1, 2.9, H-3), 1.98
(ddd, 14.1, 5.3, 2.9, H-4), 1.88 (dd, 14.1, 7.1, H-4), 2.96 (dddd, 14.1, 7.8, 7.5, 5.3, H-5),5.22 (ddd, 9.1, 7.5, 3.1,
H-6), 2.45 (dd, 14.7, 9.1, H-7), 1.70 (ddd, 14.7, 3.1, 1.4, H-7), 2.27 (ddd, 7.8, 3.9, 1.4, H-9), 1.31 (s, H3 -10), 7.79
(d, 8.8, H-2, 6), 6.71 (d, 8.8, H-3, 5); 13C-NMR (100 MHz, CD3OD): 100.1 (C-1), 96.5 (C-3), 31.1 (C-4), 40.7
(C-5), 81.7 (C-6), 48.3 (C-7), 49.0 (C-8), 53.3 (C-9), 23.8 (C-10), 55.7 (OMe-3), 56.0 (OMe-1), 122.5 (C-1),
132.8 (C-2, 6), 116.1 (C-3, 5), 163.5 (C-4), 168.1 (C-7). Tabebuia avellanedae (Bignoniaceae).60)
5-Deoxy-8-deacetyl-3-O-methyl-6-O-p-hydroxybenzoyl-1-epi-clandonensine (Compound 2) (C-3-epimer of 1)
C18H24O7: 352.1522; colorless amorphous solid; [a ]D25 56.4 (c0.035, MeOH), IR (KBr): 3550, 3400, 1708,
1656, 1607, 1511, 1260, 960; 1H-NMR (400 MHz, CD3OD): 4.70 (d, 5.5, H-1), 4.78 (dd, 5.6, 3.7, H-3), 1.60
(ddd, 14.7, 7.9, 5.6, H-4), 1.94 (m, H-4), 2.79 (ddd, 14.7, 7.7, 4.5, H-5), 5.22 (dd, 7.5, 4.5, H-6), 1.90 (m, H-7),
2.34 (dd, 14.9, 7.5, H-7), 2.14 (dd, 7.7, 5.5, H-9), 1.35 (s, H3-10), 7.88 (d, 8.8, H-2, 6), 6.80 (d, 8.8, H-3, 5);
13
C-NMR (100 MHz, CD3OD): 98.9 (C-1), 99.3 (C-3), 30.7 (C-4), 41.9 (C-5), 80.3 (C-6), 47.7 (C-7), 49.0 (C-8),
52.9 (C-9), 26.9 (C-10), 56.0 (OMe-1), 53.3 (MeO-3), 122.6 (C-1), 132.6 (C-2, 6), 116.1 (C-3, 5), 163.5 (C4), 168.5 (C-7). Tabebuia avellanedae (Bignoniaceae).60)
Shanzhilactone
C11H16O6: 244.0947; isolated as acetate; colorless needles; mp 182 C; IR (KBr): 3420, 1755, 1730; 1H-NMR (400 MHz,
CDCl3): 4.42 (dd, 12.5, 3.5, H-3), 4.37 (dd, 12.5, 9.5, H-3), 3.09 (ddd, 9.5, 6.5, 3.5, H-4), 3.16 (dd, 12.0, 6.5, H-5), 5.18 (dd,
6.5, 6.0, H-6), 2.25 (dd, 13.0, 6.5, H-7), 2.02 (dd, 13.0, 6.0, H-7), 3.34 (d, 9.5, H-9), 1.47 (s, H3-10), 3.71 (s, OMe), 2.03 (s,
OAc); 13C-NMR (100 MHz, CDCl3): 169.9 (C-1), 65.9 (C-3), 39.9 (C-4), 42.7 (C-5), 72.9 (C-6), 45.9 (C-7), 79.0 (C-8), 53.7
(C-9), 25.8 (C-10), 169.5 (C-11), 52.2 (OMe), 20.8, 170.0 (Ac). Mussaenda incana (Rubiaceae).61)
August 2009
137.
785
Piscrocin E
C11H18O5: 230.1154; colorless oil; [a ]D20 70.7 (c0.03, MeOH); UV (MeOH): 205; IR (film): 3358, 2924, 1442, 1144,
1038; 1H-NMR (300 MHz, CD3OD): 4.24 (d, 9.0, H-1) 3.44 (dd, 12.7, 2.7, H-3), 3.84 (dd, 12.7, 7.8, H-3), 1.54 (br d, 14.1,
H-4), 1.74 (m, H-4), 2.00 (m, H-5), 4.09 (br d, 9.0, H-6), 3.44 (br s, H-7), 2.14 (dd, 9.0, 7.5, H-9), 3.63 (d, 13.2, H-10),
3.92 (d, 13.2, H-10), 3.53 (dt, 7.1, 2.4, H-1), 3.95 (m, H-1), 1.21 (t, H3-2); 13C-NMR (75 MHz, CD3OD): 102.4 (C-1),
62.8 (C-3), 24.1 (C-4), 38.4 (C-5), 73.4 (C-6), 61.9 (C-7), 66.0 (C-8), 44.2 (C-9), 61.2 (C-10), 65.5 (C-1), 15.5 (C-2).
Neopicrorhiza scrophulariiflora (Scrophulariaceae).19)
138.
Piscrocin F
C21H28O9: 424.1733; white amorphous powder; [a ]D20 115.0 (c0.02, MeOH); UV (MeOH): 205, 218, 264, 292;
IR (KBr): 3357, 2974, 1710, 1597, 1515, 1285, 1030; 1H-NMR (300 MHz, CD3OD): 4.76 (d, 7.8, H-1), 4.99 (d, 3.4,
H-3), 1.76 (br d, 14.7, H-4), 1.85 (m, H-4), 2.40 (m, H-5), 5.60 (dd, 9.1, 1.1, H-6), 3.75 (br s, H-7), 2.30 (t, 8.8, H-9),
3.72 (d, 13.1, H-10), 3.98 (d, 13.1, H-10), 3.59 (ddd, 14.2, 7.1, 2.2, Ha-1), 3.79 (dd, 7.1, 2.5, Hb-1), 1.25 (t, 7.1, H32), 3.49 (ddd, 14.1, 7.1, 2.6, Ha-1), 3.96 (dd, 12.1, 2.2, Hb-1), 1.22 (t, 7.1, H3-2), 7.55 (br s, H-2), 6.84 (d, 8.4, H5), 7.56 (dd, 7.7, 2.2, H-6), 3.89 (s, OMe); 13C-NMR (75 MHz, CD3OD): 99.4 (C-1), 95.3 (C-3), 27.8 (C-4), 34.6
(C-5), 79.3 (C-6), 59.6 (C-7), 66.9 (C-8), 42.8 (C-9), 61.0 (C-10), 65.6 (C-1), 15.6 (C-2), 64.4 (C-1), 15.4 (C-2),
122.3 (C-1), 125.3 (C-2), 153.3 (C-3), 149.0 (C-4), 113.8 (C-5), 116.1 (C-6), 168.4 (C-7), 56.6 (OMe).
Neopicrorhiza scrophulariiflora (Scrophulariaceae).19)
139.
Piscrocin G
C21H28O9: 424.1733; white amorphous powder; [a ]D 91.8 (c0.03, MeOH); UV (MeOH): 205, 218, 264, 293;
IR (KBr): 3358, 2975, 1711, 1604, 1524, 1240, 1042; 1H-NMR (300 MHz, CD3OD): 4.68 (d, 7.8, H-1), 4.82 (m,
H-3), 1.64 (m, H-4), 1.81 (td, 16.2, 2.3, H-4), 2.42 (m, H-5), 5.36 (dd, 8.9, 1.1, H-6), 3.71 (br s, H-7), 2.34 (t, 7.8,
H-9), 3.69 (d, 13.1, H-10), 3.99 (d, 13.1, H-10), 3.62 (dd, 7.1, 2.3, H-1), 3.97 (dd, 7.1, 2.4, H-1), 1.25 (t, 7.1, H32), 3.57 (dd, 7.1, 2.3, H-1), 3.92 (dd, 7.1, 2.5, H-1), 1.20 (t, 7.1, H3-2), 7.56 (br s, H-2), 6.85 (d, 8.1, H-5),
7.59 (dd, 8.0, 2.0, H-6), 3.90 (s, OMe); 13C-NMR (75 MHz, CD3OD): 100.0 (C-1), 98.7 (C-3), 29.8 (C-4), 36.4
(C-5), 77.5 (C-6), 59.9 (C-7), 66.7 (C-8), 43.9 (C-9), 60.9 (C-10), 65.5 (C-1, 1), 15.6 (C-2, 2), 122.2 (C-1),
125.4 (C-2), 153.4 (C-3), 149.0 (C-4), 113.8 (C-5), 116.1 (C-6), 168.4 (C-7), 56.6 (OMe). Neopicrorhiza
scrophulariiflora (Scrophulariaceae).19)
140.
Morindacin
C10H14O5: 214.0841; colorless syrup; [a ]D26 2.0 (c0.2, MeOH); IR (KBr): 3400, 1743, 1635, 1386, 1190, 1051; 1HNMR (400 MHz, CD3OD): 3.79 (dd, 11.4, 4.5, H-1), 3.72 (dd, 11.4, 6.7, H-1), 2.96 (ddd, 6.0, 4.7, 3.7, H-4), 3.33 (dt, 7.7,
6.0, H-5), 5.40 (br d, 7.7, H-6), 5.84 (quin-like, H-7), 3.10 (m, H-9), 4.22 (ddd, 15.0, 2.4, 1.2, H-10), 4.16 (ddd, 15.0, 2.8, 1.7,
H-10), 3.90 (dd, 10.8, 4.7, H-11), 3.84 (dd, 10.8, 3.7, H-11); 13C-NMR (100 MHz, CD3OD): 60.8 (C-1), 180.9 (C-3), 45.9 (C4), 44.0 (C-5), 88.3 (C-6), 125.1 (C-7), 153.4 (C-8), 50.0 (C-9), 60.5 (C-10), 62.8 (C-11). Morinda citrifolia (Rubiaceae).62)
141.
Kankanol
C9H13ClO4: 220.0502; amorphous powder; [a ]D25 11.1 (c1.40, MeOH); IR (KBr): 3399, 3004, 1165, 1096, 1059,
1048, 955; 1H-NMR (500 MHz, CD3OD): 5.26 (d, 4.3, H-1), 5.17 (br d, ca. 3.0, H-3), 1.60 (ddd, 13.1, 5.5, 2.5, Ha -4), 1.80
(br dd, ca. 13.0, 3.0, Hb -4), 2.50 (m, H-5), 1.83 (br d, ca. 12.0, Ha -6), 2.57 (m, Hb -6), 3.80 (br s, Hb -7), 2.76 (dd, 8.0, 4.3,
H-9), 3.75 (d, 9.2, H-10), 3.88 (d, 9.2, H-10), 13C-NMR (125 MHz, CD3OD): 98.1 (C-1), 95.7 (C-3), 34.3 (C-4), 26.1 (C5), 42.3 (C-6), 79.6 (C-7), 92.7 (C-8), 54.9 (C-9), 71.5 (C-10). Cistanche tubulosa (Orobanchaceae).25)
142.
Piscrocin D
C9H14O5: 202.0841; yellow amorphous powder, [a ]D20 15.2 (c0.1, MeOH); UV (MeOH): 205; IR (KBr): 3422, 2941,
1405, 1253, 1107, 1030; 1H-NMR (300 MHz, CD3OD): 5.29 (d, 5.9, H-1) 3.51 (ddd, 11.8, 5.1, 2.1, Ha-3), 3.92 (dd, 11.8,
2.7, Hb-3), 1.62 (br dd, 14.1, 2.0, H-4), 1.78 (m, H-4), 2.45 (m, H-5), 3.95 (dd, 8.5, 3.7, H-6) 3.70 (d, 3.7, H-7), 2.18 (dd, 10.3,
5.9, H-9), 3.62 (d, 10.1, H-10), 3.78 (d, 10.1, H-10); 13C-NMR (75 MHz, CD3OD): 101.9 (C-1), 56.4 (C-3), 22.3 (C-4), 37.1
(C-5), 74.1 (C-6), 79.4 (C-7), 85.8 (C-8), 46.8 (C-9), 75.4 (C-10). Neopicrorhiza scrophulariiflora (Scrophulariaceae).19)
143.
Myopochlorin
C9H1235ClO5: 235.0373; amorphous powder; [a ]D21 71.9 (c2.63, MeOH); IR (film): 3369, 2922, 1402, 1347, 1292,
1147, 1033; 1H-NMR (400 MHz, CD3OD): 5.41 (d, 6.0, H-1), 3.74 (ddd, 13.0, 13.0, 2.0, H-3), 3.66 (ddd, 13.0, 6.0, 2.0, H3), 1.87 (ddd, 13.0, 2.0, 2.0, H-4), 1.62 (ddd, 13.0, 13.0, 6.0, H-4), 3.71 (d, 11.0, H-6), 4.53 (dd, 11.0, 2.0, H-7), 2.15 (d, 6.0,
H-9), 4.46 (d, 10.0, H-10), 3.40 (dd, 10.0, 2.0, H-10); 13C-NMR (100 MHz, CD3OD): 102.3 (C-1), 58.5 (C-3), 32.0 (C-4),
73.1 (C-5), 76.8 (C-6), 72.4 (C-7), 84.3 (C-8), 55.7 (C-9), 72.2 (C-10). Myoporum bontioides (Myoporaceae).23)
144.
6b ,7b ,8a ,10-Tetrahydroxy-cis-2-oxabicyclo[4.3.0]nonan-3-one

C9H14O6: 218.0790; white needles; mp 164165 C; [a ]D25 0.131 (c0.45, CHCl3); IR (KBr): 3381, 2927, 2855, 1713,
1466, 1380, 1095; 1H-NMR (400 MHz, CD3OD): 4.48 (dd, 12.0, 8.0, H-1), 4.33 (dd, 12.0, 6.8, H-1), 2.73 (dd, 14.4,
5.6, H-4), 2.58 (dd, 14.4, 8.0, H-4), 2.53 (dddd, 8.8, 8.0, 8.0, 5.6, H-5), 4.06 (dd, 8.0, 3.6, H-6), 3.76 (d, 3.6, H-7), 2.47
(ddd, 8.0, 8.8, 6.8, H-9), 3.73 (d, 11.2, H-10), 3.63 (d, 11.2, H-10); 13C-NMR (100 MHz, CD3OD): 68.2 (C-1), 176.3
(C-3), 33.8 (C-4), 41.0 (C-5), 79.4 (C-6), 79.9 (C-7), 82.6 (C-8), 41.2 (C-9), 66.2 (C-10). Crescentia alata (Bignoniaceae).63)
786
145.
146.
Vol. 57, No. 8

6b ,7b ,8a ,10-Tetra-p-hydroxybenzoyl-cis-2-oxabicyclo[4.3.0]nonan-3-one
C23H22O10: 458.1306; white amorphous powder; [a ]D25 56.2 (c0.83, CHCl3); UV (CHCl3): 385 (0.35),
272 (0.96), 251 (2.70); IR (CHCl3): 3390, 2925, 2854, 1714, 1606, 1464, 1089; 1H-NMR (400 MHz,
CDCl3): 4.70 (dd, 12.4, 6.4, H-1), 4.55 (dd, 12.4, 5.6, H-1), 2.91 (dd, 15.6, 6.8, H-4), 2.79 (dd, 15.6, 7.2, H4), 3.16 (dddd, 11.6, 7.2, 6.8, 7.2, H-5), 5.50 (dd, 7.2, 4.4, H-6), 6.40 (d, 4.4, H-7), 3.33 (ddd, 11.6, 6.4, 5.6,
H-9), 5.36 (d, 12.4, H-10), 5.10 (d, 12.4, H-10), 7.61 (d, 8.4, H-2, 6), 7.46 (d, 8.4, H-3, 5), 7.77 (d, 8.8,
H-2, 6), 7.53 (d, 8.8, H-3, 5), 7.95 (d, 8.4, H-2, 6), 7.66 (d, 8.4, H-3, 5), 7.73 (d, 8.4, H-2, 6),
7.54 (d, 8.4, H-3, 5); 13C-NMR (100 MHz, CDCl3): 65.7 (C-1), 170.6 (C-3), 32.2 (C-4), 38.2 (C-5), 77.0
(C-6), 75.9 (C-7), 88.1 (C-8), 42.0 (C-9), 63.5 (C-10), 128.0 (C-1), 131.0 (C-2, 6), 132.1 (C-3, 5),
129.1 (C-4), 164.9 (C-7), 127.7 (C-1), 131.2 (C-2, 6), 132.1 (C-3, 5), 129.4 (C-4), 164.4 (C-7),
127.8 (C-1), 131.3 (C-2, 6), 132.4 (C-3, 5), 129.6 (C-4), 164.4 (C-7), 127.6 (C-1), 131.5 (C-2,
6), 132.2 (C-3, 5), 129.0 (C-4), 165.0 (C-7). Crescentia alata (Bignoniaceae).63)
1b ,6b ,7a ,8a ,10-Pentahydroxy-cis-2-oxabicyclo[4.3.0]nonane
C9H16O6: 220.0947; white amorphous powder; [a ]D25 78.2 (c0.11, CHCl3); IR (CHCl3): 3382, 2918, 2851, 1043; 1HNMR (400 MHz, CDCl3): 5.40 (d, 5.2, H-1), 3.90 (ddd, 12.0, 12.0, 2.8, H-3), 3.63 (ddd, 12.0, 5.2, 2.0, H-3), 1.84 (dddd,
14.8, 12.0, 6.0, 1.2, H-4), 1.71 (dd, 14.8, 2.8, H-4), 2.28 (dddd, 10.0, 10.0, 6.0, 2.0, H-5), 3.99 (dd, 10.0, 10.0, H-6), 4.14 (dd,
10.0, 2.0, H-7), 2.42 (dd,10.0, 5.2, H-9), 4.49 (d, 10.4, H-10), 3.51 (dd, 10.4, 2.0, H-10); 13C-NMR (100 MHz, CDCl3): 100.1
(C-1), 55.8 (C-3), 21.1 (C-4), 35.2 (C-5), 75.6 (C-6), 73.6 (C-7), 85.0 (C-8), 44.3 (C-9), 72.4 (C-10). Crescentia alata
(Bignoniaceae).63)
147.
6b -Hydroxy-2-oxabicyclo[4.3.0]non-8-en-1-one
C9H12O3: 168.0786; yellow oil; [a ]D25 0.68 (c0.06, CHCl3); UV (CHCl3): 246 (1.84); IR (CHCl3): 3365, 1727, 1652, 1603,
1043; 1H-NMR (400 MHz, CDCl3): 4.43 (ddd, 11.2, 4.8, 2.8, H-3), 4.27 (ddd, 11.2, 12.0, 2.8, H-3), 1.67 (dddd, 13.6, 12.0, 12.0,
4.8, H-4), 2.20 (m, H-4), 2.87 (m, H-5), 4.20 (dt, 7.6, 8.8, H-6), 2.65 (ddd, 16.8, 8.0, 1.2, H-7), 2.54 (ddd, 16.8, 8.8, 1.6, H-7),
2.20 (s, H3-10); 13C-NMR (100 MHz, CDCl3): 164.1 (C-1), 69.4 (C-3), 28.3 (C-4), 50.1 (C-5), 78.6 (C-6), 46.9 (C-7), 157.0 (C8), 122.6 (C-9), 17.0 (C-10). Crescentia alata (Bignoniaceae).63)
148.
Tarennin (artifact)
C12H14O6: 254.0790; amorphous powder; [a ]D23 87.2 (c0.45, MeOH); UV (MeOH): 342 (2.38), 325 (2.45); IR (KBr):
3431,1690, 1637, 1624, 1558, 1408, 1271, 1163, 1038, 743; 1H-NMR (400 MHz, CD3OD): 5.28 (d, 3.6, H-1), 7.40 (s, H-3),
3.21 (m, H-5), 2.83 (dd, 18.0, 7.8, H-6), 2.35 (d, 18.0, H-6), 6.57 (br s, H-7), 3.15 (br s, H-9), 3.82 (dq, 9.7, 7.1, H-1), 3.59
(dq, 9.7, 7.1, H-1), 1.18 (t, 7.1, H3-2); 13C-NMR (100 MHz, CD3OD): 100.3 (C-1), 152.9 (C-3), 113.6 (C-4), 34.8 (C-5),
40.1 (C-6), 142.0 (C-7), 140.4 (C-8), 48.4 (C-9), 171.4 (C-10), 172.0 (C-11), 65.8 (C-1), 15.4 (C-2). Tarenna attenuata (Rubiaceae).36)
149.
Plumericin
C15H14O6: 290.0790; colorless crystals; mp 205208 C (dec); [a ]D20 179.0 (c14.6, CHCl3); UV
(MeCN): 237 sh (4.05), 213 sh (4.27), 200 (4.32); IR (CHCl3): 1755, 1796, 1635, 1524; 1H-NMR
(500 MHz, CDCl3): 5.55 (d, 6.0, H-1), 7.44 (s, H-3), 4.01 (td, 9.5, 6.0, H-5), 5.65 (dd, 5.5, 2.2, H-6), 6.05
(dd, 5.5, 2.2, H-7), 3.45 (dd, 9.5, 6.0, H-9), 5.11 (s, H-10), 7.15 (dq, 7.5, 1.5, H-13), 2.10 (d, 7.5, H3-14),
3.75 (s, OMe); 13C-NMR (125 MHz, CDCl3): 102.3 (C-1), 152.3 (C-3), 104.6 (C-4), 38.4 (C-5), 126.3 (C6), 141.1 (C-7), 109 (C-8), 53.7 (C-9), 80.3 (C-10), 127.4 (C-11), 168.2 (C-12), 145.6 (C-13), 16.2 (C14), 166.6 (C-15), 51.7 (OMe). Plumeria rubra.64) This revised structure was not in agreement with vibrational CD spectra.65)
150.
Isoplumericin
C15H14O6: 290.0790; colorless crystals; mp 207211 C; [a ]D20 179.0 (c14.6, CHCl3); UV (MeCN):
238 sh (4.07), 210 (4.30); 1H-NMR (500 MHz, CDCl3): 5.55 (d, 6.0, H-1), 7.44 (s, H-3), 4.01 (td, 9.5, 6.0,
H-5), 5.65 (dd, 5.5, 2.2, H-6), 6.05 (dd, 5.5, 2.2, H-7), 3.45 (dd, 9.5, 6.0, H-9), 5.11 (s, H-10), 6.84 (dq,
7.5, 1.5, H-13), 2.35 (d, 6.5, H3-14), 3.75 (s, OMe); 13C-NMR (125 MHz, CDCl3): 101.3 (C-1), 152.3 (C3), 104.1 (C-4), 38.4 (C-5), 126.1 (C-6), 141.1 (C-7), 109.2 (C-8), 51.7 (C-9), 83.7 (C-10), 125.4 (C-11),
168.2 (C-12), 145.6 (C-13), 14.8 (C-14), 166.6 (C-15), 51.6 (OMe). Plumeria rubra.64)
151.
Prismatomerin
C20H16O7: 368.0896; white needles; mp 134135 C, [a ]D25 136.0 (c0.01, EtOH); UV (CDCl3): 317 (4.07); IR
(KBr); 3512, 3123, 2962, 1732, 1696, 1644; 1H-NMR (500 MHz, CDCl3): 5.67 (d, 5.8, H-1), 7.50 (s, H-3), 4.08 (tt, 9.5,
2.0, H-5), 6.07 (dd, 5.4, 2.1, H-6), 5.67 (overlapped, H-7), 3.56 (dd, 9.5, 5.8, H-9), 5.25 (br s, H-10), 7.81 (br s, H-13),
3.81 (s, H-15), 7.71 (d, 8.6, H-2, 6), 6.97 (d, 8.6, H-3, 5), 5.73 (br s, HO-4); 13C-NMR (125 MHz,CDCl3): 102.4 (C1), 152.9 (C-3), 109.6 (C-4), 38.5 (C-5), 141.1 (C-6), 126.5 (C-7), 104.5 (C-8), 54.2 (C-9), 82.0 (C-10), 120.2 (C-11),
170.2 (C-12), 144.4 (C-13), 166.8 (C-14), 51.7 (OMe), 126.2 (C-1), 133.3 (C-2, 6), 116.3 (C-3, 5), 158.9 (C-4).
Prismatomeris tetrandra (Rubiaceae).65,66)
August 2009
787
152.
1,5-Dihydroxy-3,8-epoxyvalechlorine A
C12H15ClO6: 290.0557; colorless oil; [a ]D20 86.2 (c0.1, MeOH); IR (KBr): 3436, 2920, 1736, 1628, 1247, 1108, 963;
1
H-NMR (600 MHz, CDCl3): 5.60 (d, 3.2, H-1), 5.30 (s, H-3), 2.59 (dd, 14.3, 7.3, H-6), 2.03 (dd, 14.3, 2.6, H-6), 4.95 (dd,
7.3, 2.6, H-7), 2.64 (d, 3.2, H-9), 3.78 (d, 11.5, H-10), 3.73 (d, 11.5, H-10), 5.38 (s, H-11), 5.12 (s, H-11), 2.08 (s, OAc);
13
C-NMR (150 MHz, CDCl3): 90.5 (C-1), 94.1 (C-3), 151.6 (C-4), 77.4 (C-5), 46.5 (C-6), 74.6 (C-7), 82.5 (C-8), 46.6 (C9), 45.5 (C-10), 108.3 (C-11), 21.0, 169.6 (OAc). Valeriana wallichii (Valerianaceae).67)
153.
Rupesin E
C15H22O5: 282.1467; colorless oil; [a ]D20 22.0 (c0.89, MeCOMe); IR (KBr): 3477, 1742, 1670; 1H-NMR
(400 MHz, CDCl3): 6.18 (d, 3.3, H-1), 5.08 (s, H-3), 3.00 (dd, 8.0, 4.2, H-5), 1.92 (m, H-6), 1.77 (m, H-6), 3.63 (m, H7), 2.33 (dd, 4.2, 3.3, H-9), 1.26 (s, H3-10), 4.87 (br s, H-11), 4.77 (br s, H-11), 2.13 (m, H2-2), 1.92 (m, H-3), 0.88
(d, 1.8, H3-4, 5); 13C-NMR (100 MHz, CDCl3): 90.5 (C-1), 93.3 (C-3), 149.4 (C-4), 36.8 (C-5), 43.0 (C-6), 78.1 (C7), 82.8 (C-8), 41.8 (C-9), 19.5 (C-10), 107.9 (C-11), 171.8 (C-1), 43.4 (C-2), 25.8 (C-3), 22.7 (C-4, 5). Patrinia
rupestris.68)
154.
8-Methylvalepotriate
C27H34O9; 502.2202; yellow oil; [a ]D20 50.0 (c0.1, MeOH); IR (KBr): 3436, 1740, 1627, 1599, 1516, 1458,
1270, 1157; 1H-NMR (600 MHz, CDCl3): 6.02 (d, 3.7, H-1), 6.34 (s, H-3), 2.93 (m, H-5), 1.98 (m, H-6), 2.10
(m, H-6), 5.33 (td, 5.2, 2.2, H-7), 2.10 (m, H-8), 2.19 (m, H-9), 1.11 (d, 6.7, H3-10), 4.57 (d, 12.1, H-11), 4.42 (d,
12.1, H-10), 2.07 (s, Ac), 2.14 (m, H-2), 2.11 (m, H-3), 0.99 (d, 6.7, H3-4), 0.98 (d, 6.7, H3-5), 7.03 (d, H-2),
6.92 (d, 8.3, H-5), 7.08 (dd, 8.3, 1.7, H-6), 3.93 (s, MeO-3), 7.61 (d, 15.8, H-7), 6.28 (d, 15.8, H-8); 13CNMR (150 MHz, CDCl3): 91.0 (C-1), 139.9 (C-3), 113.4 (C-4), 32.2 (C-5), 37.3 (C-6), 76.7 (C-7), 39.2 (C-8),
45.8 (C-9), 12.9 (C-10), 64.0 (C-11), 20.9, 170.9 (Ac), 171.8 (C-1), 43.4 (C-2), 25.6 (C-3), 22.3 (C-4, 5),
126.9 (C-1), 109.4 (C-2), 146.8 (C-3), 148.0 (C-4), 114.7 (C-5), 123.0 (C-6), 55.9 (MeO-3), 145.0 (C-7),
115.4 (C-8), 166.7 (C-9). Valeriana wallichii (Valerianaceae).67)
155.
Valeriotetrate B
C34H50O14; 682.3200; colorless oil; [a ]D20 190.2 (c0.1, MeOH); 1H-NMR (600 MHz, CDCl3): 6.22 (d,
10.0, H-1), 6.68 (s, H-3), 5.75 (dd, 2.6, 2.4, H-6), 5.38 (d, 2.6, H-7), 2.89 (dd, 10.0, 2.4, H-9), 4.70 (d, 11.4,
H-10), 4.28 (d, 11.4, H-10), 4.71 (d, 12.4, H-11), 4.62 (d, 12.4, H-11), 2.03 (s, OAc), 1.95 (s, OAc), 2.31 (m,
H-2), 2.15 (m, H-3), 0.97 (d, 6.4, H-4), 0.96 (d, 6.4, H-5), 2.98 (d, 14.2, H-2), 2.80 (d, 14.2, H-2), 1.51
(s, H3-4), 1.50 (s, H3-5), 4.72 (d, 4.2, H-2), 2.24 (m, H-3), 1.00 (d, 6.4, H3-4), 0.99 (d, 6.4, H3-5), 2.34
(m, H2-7), 2.09 (m, H-8), 1.02 (d, 6.4, H3-9), 0.98 (d, 6.4, H3-10); 13C-NMR (125 MHz, CDCl3): 92.5
(C-1), 148.2 (C-3), 108.6 (C-4), 139.1 (C-5), 117.3 (C-6), 83.2 (C-7), 80.0 (C-8), 48.3 (C-9), 65.5 (C-10),
60.8 (C-11), 20.9, 170.8 (OAc-11), 22.2, 170.3 (OAc-3) 170.7 (C-1), 42.9 (C-2), 25.5 (C-3), 22.3 (C-4,
5), 168.9 (C-1), 44.1 (C-2), 79.3 (C-3), 26.4 (C-4), 26.5 (C-5), 169.6 (C-1), 76.8 (C-2), 30.0 (C-3),
18.6 (C-4), 17.1 (C-5), 173.7 (C-6), 43.0 (C-7), 25.6 (C-8), 22.3 (C-9, 10). Valeriana wallichii (Valerianaceae).67)
156.
Valeriotetrate C
C37H58O15; 742.3775; colorless needles; mp 5455 C; [a ]D20 63.8 (c0.1, MeOH); IR (KBr): 3460,
1742, 1659, 1247, 1186; 1H-NMR (600 MHz, CDCl3): 6.57 (d, 1.4, H-1), 6.61 (s, H-3), 2.60 (dd, 13.2, 6.2,
H-6), 2.11 (m, H-6), 4.93 (dd, 6.2, 2.4, H-7), 2.58 (d, 1.4, H-9), 4.27 (d, 11.4, H-10), 4.23 (d, 11.4, H-10),
4.91 (d, 12.7, H-11), 4.69 (d, 12.7, H-11), 2.29 (m, H-2), 2.08 (m, H-3), 0.98 (overlapped, H3-4), 0.99
(overlapped, H3-5), 4.79 (d, 4.8, H-2), 2.21 (m, H-3), 1.00 (overlapped, H3-4), 0.99 (overlapped, H3-5),
2.28 (m, H2-7), 2.09 (m, H-8), 0.96 (overlapped, H3-9), 0.97 (overlapped, H3-10), 4.80 (d, 4.8, H-2),
2.21 (m, H-3), 1.01 (d, 6.4, H3-4), 0.99 (d, 6.4, H3-5), 2.26 (m, H2-7), 2.09 (m, H-8), 0.96 (overlapped,
H3-9), 0.97 (overlapped, H3-10), 2.09 (s, OAc); 13C-NMR (150 MHz, CDCl3): 89.0 (C-1), 145.0 (C-3),
112.5 (C-4), 69.6 (C-5), 40.5 (C-6), 79.8 (C-7), 79.1 (C-8), 53.3 (C-9), 67.3 (C-10), 61.9 (C-11), 20.7,
170.7 (OAc),171.2 (C-1), 43.1 (C-2), 25.7 (C-3), 22.3 (C-4, 5), 169.6 (C-1), 76.6 (C-2), 29.9 (C-3),
17.3 (C-4), 18.6 (C-5), 173.0 (C-6), 43.0 (C-7), 25.6 (C-8), 22.3 (C-9, 10 ), 169.9 (C-1), 76.7 (C-2),
30.0 (C-3), 17.2 (C-4), 18.9 (C-5), 173.2 (C-6), 42.9 (C-7), 25.7 (C-8), 22.4 (C-9,10). Valeriana
wallichii (Valerianaceae).67)
157.
Valeriotriate A
C29H46O12: 586.2989; colorless oil; 1H-NMR (500 MHz, CD3COCD3): 6.55 (d, 1.8, H-1),
6.59 (s, H-3), 2.53 (dd, 13.5, 7.4, H-6), 2.06 (m, H-6), 4.95 (dd, 7.4, 7.0, H-7), 2.68 (s, H9), 3.60 (m, H2-10), 4.74 (d, 12.9, H-11), 4.80 (d, 12.9, H-11), 2.24 (m, H2-2), 2.23 (m, H3), 0.96 (d, 6.7, H3-4)a, 0.97 (d, 6.7, H3-5 )a, 4.86 (d, 4.3, H-2), 2.10 (m, H-3), 0.95 (d,
6.7, H3-4)a, 0.97 (d, 6.7, H3-5)a, 2.28 (m, H2-7), 2.02 (m, H-8), 0.96 (d, 6.7, H3-9)a,
0.99 (d, 6.7, H3-10)a, 3.55 (q, 7.0, H2-1), 1.17 (t, 7.0, H3-2), 2.05 (s, Ac); 13C-NMR
(125 MHz, CD3COCD3): 91.3 (C-1), 144.8 (C-3), 115.3 (C-4), 71.5 (C-5), 43.4 (C-6), 81.1
(C-7), 82.0 (C-8), 55.7 (C-9), 75.2 (C-10), 63.8 (C-11), 172.2 (C-1), 44.3 (C-2), 27.1 (C3), 23.2 (C-4, 5), 170.8 (C-1), 77.9 (C-2), 31.4 (C-3 ), 19.8 (C-4), 17.5 (C-5), 173.6
(C-6), 44.2 (C-7), 26.9 (C-8), 23.3 (C-9, 10), 68.2 (C-1), 16.0 (C-2), 21.6, 171.6
(Ac). Valeriana jatamansi (Valerianaceae).69)
788
158.
Vol. 57, No. 8

Valeriotriate B
C27H42O12: 558.2676; colorless oil; 1H-NMR (500 MHz, CD3COCD3): 6.65 (d, 1.8, H-1), 6.57 (s, H3), 2.37 (dd, 13.2, 5.0, H-6), 2.11 (m, H-6), 3.82 (dd, 7.5, 5.1, H-7), 2.72 (d, 1.8, H-9), 4.14 (d, 11.9,
H-10), 4.04 (d, 11.9, H-10), 4.74 (d, 12.5, H-11), 4.78 (d, 12.5, H-11), 2.28 (m, H2-2), 2.08 (m, H-3),
0.97 (d, 6.5, H3-4)a, 0.99 (d, 6.5, H3-5 )a, 4.80 (d, 4.3, H-2), 2.09 (m, H-3), 0.94 (d, 6.5, H3-4)a,
0.96 (d, 6.5, H3-5)a, 2.29 (m, H2-7), 2.24 (m, H-8), 0.97 (d, 6.5, H3-9)a, 0.98 (d, 6.5, H3-10)a, 2.05
(s, Ac) a: may be exchangeable. 13C-NMR (125 MHz, CD3COCD3): 89.6 (C-1), 143.4 (C-3), 115.9 (C4), 69.3 (C-5), 43.4 (C-6), 72.0 (C-7), 79.2 (C-8), 55.6 (C-9), 66.7 (C-10), 62.7 (C-11), 171.6 (C-1),
43.4 (C-2), 26.4 (C-3), 22.6 (C-4, 5), 170.2 (C-1), 77.3 (C-2), 30.7 (C-3 ), 19.1 (C-4), 18.2 (C5), 173.1 (C-6), 43.4 (C-7), 26.2 (C-8), 22.5 (C-9, 10), 20.8, 171.1 (Ac). Valeriana jatamansi (Valerianaceae).69)
159.
Rupesin A
C20H27ClO7: 414.1445; yellow oil; [a ]D20 155.0 (c0.40, MeOH); UV (MeOH): 303 (4.30); IR (KBr): 1766,
1735, 1708, 1602, 753; 1H-NMR (400 MHz, CDCl3): 6.37 (d, 8.1, H-1), 7.05 (s, H-3), 6.01 (s, H-6), 3.49 (dd, 8.1,
1.8, H-9), 3.83 (d, 7.8, H-10), 3.60 (d, 7.8, H-10), 4.82 (d, 9.3, H-11), 4.76 (d, 9.3, H-11), 2.33 (m, H-2, 2), 2.06
(m, H-2, 2), 2.18 (m, H-3, 3), 1.01 (d, 5.1, H-4, 4), 0.93 (d, 4.8, H-5, 5); 13C-NMR (100 MHz, CDCl3): 92.9
(C-1), 154.4 (C-3), 109.7 (C-4), 165.3 (C-5), 119.1 (C-6), 204.1 (C-7), 76.1 (C-8), 44.1 (C-9), 44.2 (C-10), 60.0
(C-11), 170.7 (C-1), 43.4 (C-2), 25.9 (C-3), 22.6 (C-4), 22.5 (C-5), 173.1 (C-1), 43.2 (C-2), 25.9 (C-3),
22.5 (C-4), 22.4 (C-5). Patrinia rupestris (Valerianaceae).68)
160.
Rupesin C
C25H3935ClO9: 518.2448; colorless prisms; mp 120121 C; [a ]D20 61.8 (c1.6, MeOH); IR (KBr):
3470, 1759, 1722, 1664; 1H-NMR (400 MHz, CDCl3): 6.50 (d, 5.4, H-1), 6.52 (s, H-3), 2.55 (dd, 15.0, 9.9,
H-6), 4.89 (dd, 12.9, 6.6, H-7), 3.03 (d, 2.0, H-9), 3.60 (d, 11.7, H-10), 3.70 (d, 11.7, H-10), 4.67 (d, 12.3,
H-11), 4.74 (d, 12.3, H-11), 2.19 (m, H2-2, 2, 2), 2.11 (m, H-3, 3, 3), 0.96 (d, 6.6, H3-4, 5, 4, 5,
4, 5); 13C-NMR (100 MHz, CDCl3): 89.5 (C-1), 143.2 (C-3), 113.8 (C-4), 70.9 (C-5), 41.3 (C-6), 79.7
(C-7), 80.6 (C-8), 54.4 (C-9), 49.7 (C-10), 61.5 (C-11), 171.0 (C-1), 43.6 (C-2), 25.9 (C-3, 3, 3), 22.5
(C-4, 5, 4, 5, 4, 5), 173.1 (C-1), 43.4 (C-2), 173.3 (C-1), 43.3 (C-2). Patrinia rupestris (Valerianaceae).68)
161.
Rupesin D
C25H38O9: 482.2515; colorless prisms; mp 8485 C; [a ]D20 117.8 (c1.40, MeOH); IR (KBr): 3481,
1760, 1720, 1663, 1080; 1H-NMR (400 MHz, CDCl3): 6.08 (d, 2.4, H-1), 6.62 (s, H-3), 1.99 (dd, 13.2,
10.2, H-6), 2.79 (dd, 13.2, 7.0, H-6), 4.87 (dd, 10.2, 7.0, H-7), 2.91 (d, 2.4, H-9), 2.82 (d, 5.0, H-10), 3.12
(d, 5.0, H-10), 4.75 (d, 12.3, H-11), 4.90 (d, 12.3, H-11), 2.19 (m, H-2, 2, 2), 2.12 (m, H-3), 0.96 (d,
6.6, H-4, 5, 4, 5, 4, 5), 2.11 (m, H-3, 3); 13C-NMR (100 MHz, CDCl3): 88.1 (C-1), 144.4 (C-3),
111.6 (C-4), 69.3 (C-5), 40.2 (C-6), 72.6 (C-7), 62.0 (C-8), 47.8 (C-9), 48.7 (C-10), 60.7 (C-11), 170.7 (C1), 42.9 (C-2, 2), 25.4 (C-3, 3), 22.1 (C-4, 5, 4, 5, 4, 5), 173.1 (C-1), 171.5 (C-1), 43.7 (C-2).
Patrinia rupestris (Valerianaceae).68)
162.
Rupesin B
C22H31ClO8: 458.1707; colorless oil; 1H-NMR (400 MHz, CDCl3): 6.20 (d, 9.9, H-1), 6.63 (s, H-3), 5.69 (t, 2.8,
H-6), 5.42 (d, 2.8, H-7), 2.89 (dd, 9.9, 2.4, H-9), 3.93 (d, 11.2, H-10), 3.73 (d, 11.2, H-10), 4.65 (d, 12.4, H-11),
4.58 (d, 12.4, H-11), 2.25 (m, H2-2), 2.11 (m, H-3), 0.96 (d, 6.6, H-4, 5), 2.12 (m, H2-2), 2.11 (m, H-3), 0.96
(d, 6.6, H3-4,5), 2.13 (s, Ac); 13C-NMR (100 MHz, CDCl3): 92.4 (C-1), 148.1 (C-3), 108.9 (C-4), 139.6 (C-5),
117.3 (C-6), 83.5 (C-7), 80.4 (C-8), 49.5 (C-9), 48.6 (C-10), 60.4 (C-11), 170.6 (C-1), 43.2 (C-2), 25.6 (C-3),
22.1 (C-4, 5), 170.0 (C-1), 43.1 (C-2), 25.6 (C-3), 22.1 (C-4, 5), 173.1, 20.9 (Ac). Patrinia rupestris (Valerianaceae).68)
Group 6 (Bis- and tetrakis-iridoid glycosides)
163.
Dipsanoside C
234.4; IR (KBr): 3431 , 1701, 1637, 1292, 1074; 1H- NMR (500 MHz, CD3OD): (unit a) 5.50 (d,
6.0, H-1), 7.38 (s , H-3), 2.97 (br q, 5.5, H-5), 1.7 (dddd, 14.0 , 6.0, 4.0, 2.0, H-6), 1.95 (ddd, 14.0,
6.0, 6.0, H-6), 4.93 (dd, 6.0, 4.0, H-7), 5.70 (ddd, 17.5, 10.5, 9.0, H-8), 2.67 (ddd, 9.0, 6.0, 5.5, H9), 5.24 (d, 17.5, H-10), 5.20 (d, 10.5, H-10), 4.02 (ddd, 7.0, 5.5, 5.0, H-12), 3.72 (dd, 8.0, 5.0, H13), 3.80 (dd, 8.0, 7.0, H-13), 3.50 (dd, 11.0, 5.0, H-14), 3.45 (dd, 11.0, 5.5, H-14), 4.63 (d, 8.0,
H-1), 3.14 (dd, 9.0, 8.0, H-2), 3.31 (t, 8.5, H-3 ), 3.203.28 (H-4, 5), 3.61 (dd, 12.0, 5.5, H6), 3.80 (br d, 11.5, H-6); (unit b) 5.27 (d, 4.0, H-1), 7.36 (s, H-3), 3.06 (br q, 8.0, H-5), 1.82
(ddd, 14.0, 8.0, 4.0, H-6), 2.25 (dd, 14.0, 8.0, H-6), 5.13 (dd, 8.0, 4.0, H-7), 2.032.09 (m, H-8),
2.12 (ddd, 9.0, 8.0, 4.0, H-9), 1.01 (d, 7.0, H3-10), 3.64 (s, OMe), 4.60 (d, 8.0, H-1), 3.14 (dd,
8.5, 8.0, H-2), 3.31 (t, 8.5, H-3), 3.283.20 (H-4, 5),, 3.61 (dd, 12.0, 5.5, H-6), 3.80 (br d,
11.5, H-6); 13C-NMR (125 MHz, CD3OD): (unit a) 97.7 (C-1), 153.5 (C-3), 113.5 (C-4), 30.0
(C-5), 35.2 (C-6), 104.8 (C-7), 135.8 (C-8), 45.4 (C-9), 119.8 (C-10), 168.4 (C-11), 77.7 (C-12),
68.1 (C-13), 64.1 (C-14), 100.2 (C-1), 74.7 (C-2), 78.0 (C-3), 71.6 (C-4), 78.4 (C-5), 62.8 (C6); (unit b) 97.2 (C-1), 152.3 (C-3), 111.8 (C-4), 32.3 (C-5), 40.4 (C-6), 78.6 (C-7), 40.9 (C-8),
47.0 (C-9), 13.5 (C-10), 169.3 (C-11), 51.7 (OMe), 100.1 (C-1), 74.7 (C-2), 78.0 (C-3), 71.6
(C-4), 78.4 (C-5), 62.7 (C-6). Dipsacus asper.58)
August 2009
164.
789
Dipsanoside D
236.4; IR (KBr): 3408, 1697, 1570, 1290, 1074, 1018; 1H-NMR (500 MHz, CD3OD): (unit a) 5.49
(d, 5.5, H-1), 7.38 (s , H-3), 2.96 (br q, 6.0, H-5), 1.77 (ddd, 14.0, 6.0, 4.0, H-6), 1.90 (ddd, 14.0, 6.0,
6.0, H-6), 5.06 (dd, 6.0, 4.0, H-7), 5.70 (ddd, 17.5, 10.5, 9.0, H-8), 2.67 (ddd, 9.0, 6.0, 5.5, H-9), 5.24
(d, 17.5, H-10), 5.20 (d, 10.5, H-10), 4.06 (ddd, 11.5, 4.5, 3.0, H-12), 3.593.85 (overlapped, H-13),
4.04 (dd, 7.5, 4.5, H-13), 3.513.56 (overlapped, H-14), 4.63 (d, 8.0, H-1), 3.113.33 (H-25),
3.593.85 (Ha-6), 3.84 (d, 11.5, Hb-6); (unit b) 5.27 (d, 4.0, H-1), 7.36 (s, H-3), 3.06 (br q, 8.0, H5), 1.70 (ddd, 14.0, 9.0, 5.0, H-6), 2.25 (br dd, 14.0, 8.0, H-6), 5.12 (dd, 5.0, 3.5, H-7), 2.032.13
(m, H-8), 2.11 (ddd, 9.5, 8.0, 4.0, H-9), 1.02 (d, 6.5, H3-10), 3.85 (s, OMe), 4.60 (d, 8.0, H-1),
3.113.33 (H-2, 5), 3.513.56 (H-6); 13C-NMR (125 MHz, CD3OD): (unit a) 97.7 (C-1),153.4
(C-3), 113.5 (C-4), 30.0 (C-5), 32.3 (C-6), 104.5 (C-7), 135.8 (C-8), 45.4 (C-9), 119.8 (C-10), 168.4
(C-11), 77.4 (C-12), 68.0 (C-13), 63.4 (C-14), 100.2 (C-1), 74.7 (C-2), 78.0 (C-3), 71.6 (C-4),
78.4 (C-5), 62.8 (C-6); (unit b) 97.3 (C-1), 152.3 (C-3), 111.9 (C-4), 35.2 (C-5), 40.4 (C-6), 78.6
(C-7), 40.9 (C-8), 47.1 (C-9), 13.5 (C-10), 169.3 (C-11), 51.7 (OMe), 100.1 (C-1), 74.7 (C-2), 78.0
(C-3), 71.6 (C-4), 78.4 (C-5), 62.8 (C-6). Dipsacus asper.58)
165.
Dipsanoside E
C36H52O21: 820.3000; white amorphous powder; [a ]D20 28.3 (c0.198, MeOH); UV
(MeOH): 234.0; IR (KBr): 3446, 695, 1635, 1624, 1074; 1H-NMR (500 MHz, CD3OD): (unit a)
5.46 (d, 6.0, H-1), 7.38 (s, H-3), 2.94 (ddd, 9.0, 6.0, 4.0, H-5), 1.68 (ddd, 14.0, 7.0, 6.0, H-6),
1.87 (ddd, 14.0, 6.5, 4.0, H-6), 4.50 (dd, 7.0, 6.5, H-7), 5.70 (ddd, 17.0, 10.5, 8.0, H-8), 2.62
(ddd, 9.0, 8.0, 6.0, H-9) 5.24 (d, 17.0, H-10), 5.19 (d, 10.5, H-10), 3.98 (ddd, 10.5, 5.0, 1.5, H12), 3.193.32 (overlapped, H-12), 3.66 (dd, 10.0, 5.0, H-13), 4.02 (ddd, 10.5, 5.0, 1.5, H-14),
3.193.32 (overlapped, H-14), 4.63 (d, 8.0, H-1), 3.133.17 (dd , 8.0, 6.5, H-2), 3.193.32
(H-35), 3.593.68 (Ha-6), 3.833.86 (Hb-6); (unit b) 5.28 (d, 4.5, H-1), 7.35 (s, H-3),
3.07 (q, 7.5, H-5), 1.69 (ddd, 14.5, 7.5, 5.0, H-6), 2.24 (br dd, 14.5, 7.5, H-6), 5.11 (dd, 7.5, 5.0,
H-7), 2.032.06 (m, H-8), 2.18 (ddd, 9.0, 7.5, 4.5, H-9), 1.02 (d, 6.5, H3-10), 3.63 (s, OMe),
4.60 (d, 8.0, H-1), 3.133.17 (dd, 8.5, 6.5, H-2), 3.193.32 (H-35), 3.593.68 (Ha-6),
3.833.86 (Hb-6); 13C-NMR (125 MHz, CD3OD): (unit a) 97.7 (C-1), 153.3 (C-3), 113.6 (C4), 30.0 (C-5), 35.7 (C-6), 101.7 (C-7), 135.9 (C-8), 45.5 (C-9), 119.7 (C-10), 168.4 (C-11),
72.6 (C-12), 61.9 (C-13), 71.4 (C-14), 100.2 (C-1), 74.7 (C-2), 78.0 (C-3), 71.5 (C-4), 78.4
(C-5), 62.7 (C-6); (unit b) 97.2 (C-1), 152.2 (C-3), 112.0 (C-4), 32.1 (C-5), 40.5 (C-6), 78.6
(C-7), 40.9 (C-8), 46.9 (C-9), 13.4 (C-10), 169.4 (C-11), 51.7 (OMe), 100.1 (C-1), 74.6 (C-2),
78.0 (C-3), 71.4 (C-4), 78.3 (C-5), 62.6 (C-6). Dipsacus asper.58)
166.
Dipsanoside F
235.2; IR (KBr): 3388, 1693, 1631, 1074; 1H-NMR (500 MHz, CD3OD): (unit a) 5.49 (d, 6.0, H1), 7.39 (s, H-3), 2.94 (br q, 6.0, H-5), 1.68 (ddd, 14.0, 6.0, 6.0, H-6), 1.93 (ddd, 14.0, 6.0, 6.0, H6), 4.66 (q, 6.0, H-7), 5.71 (ddd, 17.0, 11.0, 8.0, H-8), 2.62 (br dd, 8.0, 6.0, H-9), 5.25 (d, 17.0, H10), 5.19 (d, 11.0, H-10), 3.793.88 (overlapped, H-12), 3.203.33 (overlapped, H-12), 3.60
(dd, 5.5, 3.0, H-13), 3.793.88 (overlapped, H-14), 3.203.33 (overlapped, H-14), 4.65 (d, 8.0,
H-1), 3.123.16 (H-2), 3.203.33 (H-35), 3.593.64 (Ha-6), 3.813.88 (Hb-6); (unit
b) 5.25 (d, 4.0, H-1), 7.36 (s, H-3), 3.08 (br ddd, 9.0, 7.5, 7.0, H-5), 1.69 (ddd, 14.0, 7.0, 5.0, H6), 2.25 (dd, 14.0, 7.5, H-6), 5.14 (br s, H-7), 2.08 (overlapped, H-8, 9), 1.01 (d, 6.0, H3-10), 3.64
(s, OMe), 4.59 (d, 8.0, H-1), 3.123.16 (H-2), 3.193.33 (H-35), 3.593.64 (Ha-6),
3.813.88 (Hb-6); 13C-NMR (125 MHz, CD3OD): (unit a) 97.7 (C-1),153.3 (C-3), 113.4 (C-4),
32.0 (C-5), 36.0 (C-6), 102.3 (C-7), 135.9 (C-8), 45.5 (C-9), 119.6 (C-10), 168.4 (C-11), 72.5 (C12), 65.0 (C-13), 72.3 (C-14), 100.3 (C-1), 74.7 (C-2), 78.4 (C-3), 71.6 (C-4), 78.4 (C-5),
62.8 (C-6); (unit b) 97.4 (C-1), 152.4 (C-3), 112.2 (C-4), 29.7 (C-5), 40.4 (C-6), 78.0 (C-7), 41.0
(C-8), 47.1 (C-9), 13.7 (C-10), 169.4 (C-11), 51.7 (OMe), 100.2 (C-1), 74.7 (C-2), 78.4 (C-3),
71.6 (C-4), 78.4 (C-5), 62.8 (C-6). Dipsacus asper.58)
167.
Dipsanoside G
C29H44O15: 632.2680; white amorphous powder, [a ]D20 3.4 (c1.277, MeOH); UV (MeOH): 235.0;
IR (KBr): 3417, 1732, 1699, 1633, 1385, 1074; 1H-NMR (500 MHz, CD3OD): (unit a) 5.45 (d, 5.5, H1), 7.35 (s, H-3), 3.13 (ddd, 8.0, 7.5, 2.0, H-5) , 1.561.58 (m, H-6), 1.921.96 (m, H-6), 5.22 (dd,
6.0, 4.0, H-7), 5.67 (ddd, 18.0, 10.0, 8.5, H-8), 2.84 (br dd, 8.5, 5.5, H-9), 5.24 (d, 18.0, H-10), 2.10 (d,
10.0, H-10), 3.25 (s, OMe), 4.60 (d, 7.5, H-1), 3.083.31 (H-25), 3.583.64 (H-6); (unit b)
3.803.88 (br q, 11.0, H-1), 4.66 (dd, 6.5, 2.0, H-3), 2.17 (dd, 9.0, 6.5, H-4), 2.432.48 (m, H-5),
1.751.82 (m, H-6), 2.10 (ddd, 7.0, 6.0, 4.5, H-6), 4.45 (br d, 4.5, H-7), 2.00 (m, H-8), 2.61 (br d, 4.0,
H-9), 0.93 (d, 7.0, H3-10), 3.64 (s, OMe); 13C-NMR (125 MHz, CD3OD): (unit a) 97.8 (C-1), 153.2 (C3), 112.1 (C-4), 29.3 (C-5), 44.3 (C-6), 104.3 (C-7), 135.8 (C-8), 44.3 (C-9), 119.8 (C-10), 168.3 (C11), 52.8 (OMe), 52.3 (OMe), 100.1 (C-1), 74.6 (C-2), 78.0 (C-3), 71.6 (C-4), 78.4 (C-5), 62.8 (C6); (unit b) 64.8 (C-1), 97.1 (C-3), 54.0 (C-4), 39.9 (C-5), 38.2 (C-6), 78.1 (C-7), 38.7 (C-8), 43.8 (C9), 12.4 (C-10), 175.1 (C-11), 53.7 (OMe). Dipsacus asper.58)
790
168.
Vol. 57, No. 8

Paederoside B
C36H44O22S2: 892.1765: yellow powder; [a ]D25 42.0 (c0.12, MeOH); UV (MeOH): 234.0 (4.13); IR
(KBr): 3427, 1709, 1657, 1628, 1159; 1H-NMR (600 MHz, CD3OD): (unit a) 5.07 (d, 8.3, H-1), 7.71 (d,
1.2, H-3), 3.05 (ddd, 8.3, 6.7, 1.2, H-5), 4.85 (d, 6.7, H-6), 6.02 (br s, H-7), 2.65 (t, 8.3, H-9), 4.96 (d,
14.9, H-10), 5.05 (d, 14.9, H-10), 2.32 (s, SMe), 4.73 (d, 7.9, H-1), 3.35 (m, H-2), 3.41 (m, H-3), 3.24
(m, H-4), 3.30 (m, H-5), 3.80 (dd, 12.1, 2.0, H-6), 3.64 (dd, 12.1, 6.4, H-6); (unit b) 5.82 (d, 1.1, H1), 7.30 (d, 1.9, H-3), 3.68 (ddd, 7.3, 6.5, 1.9, H-5), 5.58 (d, 6.5, H-6), 5.76 (s, H-7), 3.27 (dd, 7.3, 1.1,
H-9), 4.64 (d, 15.3, H-10), 4.82 (d, 15.3, H-10), 2.31 (s, SMe), 4.71 (d, 8.1, H-1), 3.22 (m, H-2), 3.60
(dd, 9.5, 8.6, H-3), 4.16 (dd, 8.6, 8.0, H-4), 3.38 (m, H-5), 3.59 (dd, 12.0, 1.7, H-6), 3.74 (dd, 12.0,
6.0, H-6); 13C-NMR (150 MHz, CD3OD): (unit a) 101.4 (C-1), 155.8 (C-3), 108.1 (C-4), 42.6 (C-5),
75.8 (C-6), 132.4 (C-7), 145.6 (C-8), 46.3 (C-9), 66.2 (C-10), 168.6 (C-11), 172.8 (C-12), 13.6 (SMe),
100.7 (C-1), 74.9 (C-2), 77.9 (C-3), 71.6 (C-4), 78.6 (C-5), 63.0 (C-6); (unit b) 93.0 (C-1), 150.1
(C-3), 106.2 (C- 4), 37.4 (C-5), 86.2 (C-6), 130.0 (C-7), 143.5 (C-8), 45.2 (C-9), 64.4 (C-10), 172.4 (C11), 172.6 (C-12), 13.7 (SMe), 99.9 (C-1), 74.6 (C-2), 75.6 (C-3), 72.4 (C-4), 77.7 (C-5), 62.6 (C6). Paederia scandens (Rubiaceae).70)
169.
Axillaroside
C33H46O20: 762.2582; white powder, [a ]D25 60.0 (c0.6, MeOH); UV (MeOH): 234 (4.24); IR (KBr): 3421,
1697, 1636; 1H-NMR (500 MHz, CD3OD): (unit a) 5.28 (d, 5.0, H-1), 7.24 (d, 1.5, H-3), 3.11 (br q, 8.0, H-5), 1.74
(ddd, 14.5, 8.0, 5.0, H-6), 2.29 (ddd, 14.5, 7.5, 1.5, H-6), 5.20 (br t, 5.5, H-7), 2.102.18 (m, H-8), 2.07 (td, 9.0,
5.0, H-9), 1.07 (d, 6.5, H3-10), 3.69 (s, OMe), 4.66 (d, 8.0, H-1), 3.22 (dd, 9.0, 8.0, H-2), 3.36 (t, 9.0, H-3), 3.28
(br t, 9.0, H-4), 3.263.38 (m, H-5), 3.66 (dd, 12.0, 6.0, H-6), 3.90 (dd, 12.0, 2.0, H-6); (unit b) 5.50 (d, 4.5, H1), 7.49 (d, 2.0, H-3), 3.283.38 (m, H-5), 2.30 (dd, 16.5, 9.0, H-6), 2.91 (dd, 16.5, 4.0, H-6), 5.66 (br dt, 17.0, 10.0,
H-8), 2.81 (br dt, 9.0, 5.0, H-9), 5.23 (dd, 10.0, 1.5, H-10), 5.27 (dd, 17.0, 1.0, H-10), 4.68 (d, 8.0, H-1), other sugar
protons appeared in the same region as that of sugar protons of unit a; 13C-NMR (125 MHz, CD3OD): (unit a) 97.6 (C1), 152.7 (C-3), 113.3 (C-4), 32.7 (C-5), 40.4 (C-6), 78.3 (C-7), 41.4 (C-8), 47.2 (C-9), 13.9 (C-10), 169.5 (C-11), 51.8
(OMe), 100.3 (C-1), 74.7 (C-2), 78.1 (C-3), 71.6 (C-4), 78.5 (C-5), 62.8 (C-6); (unit b) 97.7 (C-1), 153.7 (C-3),
110.5 (C-4), 29.1 (C-5), 35.3 (C-6), 176.1 (C-7), 134.5 (C-8), 45.4 (C-9), 120.6 (C-10), 168.0 (C-11), 100.1 (C-1),
74.8 (C-2), 78.1 (C-3), 71.7 (C-4), 78.5 (C-5), 62.8 (C-6). Strychnos axillaris (Loganiaceae).71)
170.
Incaside
C32H38O17: 694.2108; viscous oil; 1H-NMR (400 MHz, CD3OD): (unit a) 5.39 (d, 6.0, H-1), 6.31
(d, 6.3, H-3), 4.92 (d, 6.3, H-4), 4.98 (d, 3.0, H-6), 3.49 (s, H-7), 2.46 (d, 6.0, H-9), 1.50 (s, H310), 4.47 (d, 8.0, H-1), 3.28 (dd, 9.0, 8.0, H-2), 3.38 (dd, 9.2, 9.0, H-3), 3.47 (dd, 9.5, 9.2, H-4),
3.31 (m, H-5), 3.86 (dd, 12.5, 2.0, H-6), 3.67 (dd, 12.5, 5.0, H-6); (unit b) 5.19 (d, 5.0, H-1),
7.48 (d, 1.0, H-3), 2.86 (m, H-5), 2.16 (m, H-6), 1.34 (m, H-6), 1.18 (m, H-7), 1.88 (m, H-7), 2.23
(m, H-8), 1.99 (m, H-9), 4.14 (dd, 11.0, 6.5, H-10), 4.10 (dd, 11.0, 6.1, H-10), 7.60 (d, 2.0, H-2),
6.92 (d, 8.5, H-5), 7.38 (dd, 8.5, 2.0, H-6); 13C-NMR of its octaacetate (100 MHz, CDCl3): (unit
a) 95.8 (C-1), 141.6 (C-3), 106.8 (C- 4), 73.3 (C-5), 77.8 (C-6), 63.1 (C-7), 66.8 (C-8), 55.8 (C-9),
17.4 (C-10), 101.4 (C-1), 71.4 (C-2), 72.8 (C-3), 68.3 (C-4), 71.9 (C-5), 61.8 (C-6); (unit b)
87.8 (C-1), 152.0 (C-3), 112.8 (C-4), 35.0 (C-5), 29.7 (C-6), 33.5 (C-7), 42.5 (C-8), 45.0 (C-9),
66.2 (C-10), 170.7 (C-11), 122.8 (C-1), 120.5 (C-2), 145.1 (C-3), 151.4 (C-4), 114.3 (C-5),
124.2 (C-6), 166.7 (C-7), 20.4, 20.52, 20.63, 20.92, 168.4, 168.8, 169.3, 169.4, 169.7,
170.3, 171.12 ( 8Ac). Mussaenda incana (Rubiaceae).72)
171.
Dipsanoside A
C66H90O37: 1474.5159; white amorphous powder; UV (MeOH): 235.8 (3.2); IR
(KBr): 3399, 1693, 1637; 1H-NMR (500 MHz, CD3OD): (unit a1) 5.52 (d, 4.0,
H-1), 7.42 (s, H-3), 2.95 (br m, H-5), 3.16 (dd, 9.0, 8.0, H-6), 2.33 (dd, 8.5, 6.0,
H-6), 6.71 (dd, 7.0, 6.5, H-7), 5.72 (ddd, 18.0, 10.0, 8.0, H-8), 2.51 (ddd, 7.3,
6.4, 6.0, H-9), 5.32 (d, 17.0, H-10), 5.25 (d, 10.5, H-10), 4.61 (d, 8.0, H-1),
3.143.35 (H-2, 3, 4, 5), 3.583.66 (H-6), 3.823.86 (H-6); (unit b1)
5.12 (d, 4.0, H-1), 7.38 (s, H-3), 3.06 (br q, 8.0, H-5), 1.71 (ddd, 13.5, 8.0, 5.0,
H-6), 2.26 (br dd, 14.5, 7.0, H-6), 5.21 (d, 5.5, H-7), 2.14 (m, H-8), 2.01 (ddd,
7.0, 5.0, 4.0, H-9), 1.03 (d, 6.5, H3-10), 3.64 (s, OMe), sugar protons appeared at
the same values at that of unit a1; (unit a2) 5.43 (d, 5.5, H-1), 7.49 (s, H-3), 4.05
(d, 5.5, H-5), 9.26 (s, H-7), 5.57 (ddd, 17.5, 10.0, 7.5, H-8), 2.75 (ddd, 8.5, 5.7,
5.5, H-9), 4.99 (d, 19.5, H-10), 4.96 (d, 11.5, H-10), sugar protons appeared at
the same values as that of unit a1; (unit b2) 5.20 (d, 5.5, H-1), 7.39 (s, H-3), 2.96
(ddd, 10.0, 9.5, 7.5, H-5), 1.55 (ddd, 9.0, 8.5, 4.5, H-6), 2.08 (dd, 14.0, 8.5, H6), 5.13 (d, 6.0, H-7), 2.14 (m, H-8), 1.90 (ddd, 7.5, 7.0, 5.0, H-9), 0.95 (d, 6.5,
H3-10), 3.64 (s, OMe), sugar protons appeared at the same values at that of unit
a1; 13C-NMR (125 MHz, CD3OD): (unit a1) 98.3 (C-1), 154.1 (C-3), 113.1 (C4), 32.9 (C-5), 29.6 (C-6), 156.1 (C-7), 135.5 (C-8), 46.6 (C-9), 120.6 (C-10),
168.2 (C-11), 101.2 (C-1), 74.7 (C-2), 78.0 (C-3), 71.6 (C-4), 78.3 (C-5),
62.8 (C-6); (unit b1) 97.9 (C-1), 153.2 (C-3), 112.6 (C-4), 33.6 (C-5), 40.4 (C6), 78.6 (C-7), 41.4 (C-8), 47.1 (C-9), 14.3 (C-10), 169.4 (C-11), 51.9 (OMe),
99.6 (C-1), 74.7 (C-2), 78.2 (C-3), 71.6 (C-4), 78.4 (C-5), 62.8 (C-6); (unit
b1) 97.2 (C-1), 151.9 (C-3), 109.8 (C- 4), 30.7 (C-5), 143.7 (C-6), 197.2 (C-7),
135.4 (C-8), 45.3 (C-9), 119.6 (C-10), 168.2 (C-11), 101.2 (C-1), 74.6 (C-2),
78.0 (C-3), 71.5 (C-4), 78.3 (C-5), 62.8 (C-6); (unit b2) 97.7 (C-1), 152.7 (C3), 111.1 (C-4), 33.0 (C-5), 40.3 (C-6), 77.8 (C-7), 41.1 (C-8), 46.9 (C-9), 14.2
(C-10), 169.4 (C-11), 51.8 (OMe), 100.4 (C-1), 74.7 (C-2), 78.2 (C-3), 71.6
(C-4), 78.4 (C-5), 62.8 (C-6). Dipsacus asper.73)
August 2009
172.
791
Dipsanoside B
C66H90O37: 1474.5159; white amorphous powder; 1H-NMR (500 MHz, CD3OD):
(unit a1) 5.34 (d, 6.5, H-1), 7.60 (s, H-3), 2.93 (d, 4.0, H-5), 1.31 (d, 6.5, H2-6), 6.30
(t, 8.0, H-7), 5.37 (ddd, 17.5, 11.0, 6.5, H-8), 2.67 (ddd, 6.1, 5.8, 4.6, H-9), 5.02 (d,
11.0, H-10), 5.08 (d, 17.5, H-10), 4.66 (d, 8.0, H-1), 3.113.33 (H-2, 3, 4, 5),
3.603.64 (H-6), 3.803.86 (H-6); (unit b1) 5.15 (d, 5.5, H-1), 7.37 (s, H-3),
3.04 (dd, 8.0, 8.0, H-5), 1.59 (ddd, 14.0, 8.5, 5.0, H-6), 2.16 (dd, 14.0, 8.0, H-6),
5.165.18 (d, 6.0, H-7), 2.02 (m, H-8), 2.09 (ddd, 8.0, 7.0, 6.5, H-9), 1.03 (d, 6.5,
H3-10), 3.25 (s, OMe), 4.60 (d, 8.0, H-1), other sugar protons appeared at the same
values at that of sugar protons of unit a1; (unit a2) 5.46 (d, 5.5, H-1), 7.47 (s, H-3),
4.06 (d, 6.0, H-5), 10.00 (s, H-7), 5.71 (ddd, 17.5, 10.5, 8.0, H-8), 2.67 (ddd, 7.5,
6.0, 5.5, H-9), 5.22 (d, 11.0, H-10), 5.27 (d, 17.5, H-10), 4.63 (d, 8.0, H-1), other
sugar protons appeared at the same values at that of unit a1; (unit b2) 5.24 (d, 5.0, H1), 7.37 (s, H-3), 2.90 (ddd, 8.5, 8.0, 7.0, H-5), 1.691.74 (m, H-6), 2.24 (dd, 14.0,
8.5, H-6), 5.025.10 (d, 6.0, H-7), 2.02 (m, H-8), 1.91 (ddd, 8.5, 6.5, 5.5, H-9),
1.01 (d, 6.5, H3-10), 3.25 (s, OMe), 4.60 (d, 8.0, H-1), other sugar protons appeared
at the same values at that of sugar protons of unit a1; 13C-NMR (125 MHz, CD3OD):
(unit a1) 97.5 (C-1), 154.9 (C-3), 110.4 (C-4), 33.0 (C-5), 21.4 (C-6), 150.8 (C-7),
135.4 (C-8), 45.8 (C-9), 120.5 (C-10), 168.0 (C-11), 100.3 (C-1), 74.6 (C-2), 78.0
(C-3), 71.5 (C-4), 78.4 (C-5), 62.8 (C-6); (unit b1) 97.8 (C-1), 152.8 (C-3), 113.1
(C-4), 33.0 (C-5), 40.6 (C-6), 78.7 (C-7), 41.2 (C-8), 47.1 (C-9), 14.2 (C-10), 169.4
(C-11), 51.9 (OMe), 100.2 (C-1), 74.7 (C-2), 78.0 (C-3), 71.6 (C-4), 78.4 (C-5),
62.8 (C-6); (unit a2) 98.0 (C-1), 154.0 (C-3), 110.0 (C-4), 34.2 (C-5), 141.1 (C-6),
192.1 (C-7), 135.2 (C-8), 45.2 (C-9), 120.1 (C-10), 167.7 (C-11), 100.1 (C-1), 74.6
(C-2), 78.0 (C-3), 71.4 (C-4), 78.4 (C-5), 62.6 (C-6); (unit b2) 97.5 (C-1), 152.6
(C-3), 113.1 (C-4), 32.6 (C-5), 40.2 (C-6), 77.3 (C-7), 41.0 (C-8), 46.8 (C-9), 14.1
(C-10), 169.4 (C-11), 51.9 (OMe), 100.2 (C-1), 74.7 (C-2), 78.2 (C-3), 71.6 (C4), 78.4 (C-5), 62.8 (C-6). Dipsacus asper.73)
Fig. 1
cally listed in Table 2.

In spite of exhaustive efforts, some new iridoids and secoiridoids may be omitted in the list because of non-availability of the published papers and hence this review should not
be used as the only source of new iridoids and secoiridoids
reported during the period (20052008) of the review.
Biological and Pharmacological Activity of Naturally Occurring Iridoids and Secoiridoids

At present a good number of plant extracts containing iridoids/secoiridoids as chemical constituents are used in
preparation of bitter tonics, sedatives, febrifuges, cough medicines, anti-inflammatory, antirheumatic, antiulcer, hypo and
792
Table 2.
Vol. 57, No. 8

Alphabetical Index of Iridoids Cited in Table 1
6-O-Acetylantirrinoside 4
8-O-Acetylharpagide-6-O-b -glucoside 8
Alstonoside 133
Axillaroside 169
10-O-Benzoyl-10-O-deacetylasperuloside 100
10-O-Benzoyl-10-O-deacetyldaphylloside 91
10-O-Benzoyl-10-O-deacetyl-11-demethoxy-11-ethoxydaphylloside 92
6-O-(3-O-Benzoyl) a -L-rhamnopyranosylcatalpol 28
6-O-Caffeoylharpagide 11
6-O-[(E)-Caffeoyl]-deacetylasperulosidic acid methyl ester 88
6-O-E-Cinnamoyl-E-harpagoside 19
6-O-(3-O-E-Cinnamoyl)-a -L-rhamnopyranosylcatalpol 29
6-O-(3-O-Z-Cinnamoyl)-a -L-rhamnopyranosylcatalpol 30
Citrifoside 2
(Compound 1) 5-Deoxy-8-deacetyl-3-O-methyl-6-O-p-hydroxybenzoyl-1,
3-di-epi-clandonensine 134
(Compound 2) 5-Deoxy-8-deacetyl-3-O-methyl-6-O-p-hydroxybenzoyl-1epi-clandonensine 135
10-O-(E)-p-Coumaroyl deacetylasperulosidic acid 49
10-O-(Z)-p-Coumaroyl desacetylasperulosidic acid 50
10-O-Coumaroyl-10-O-deacetylasperuloside 99
10-O-p-Coumaroyl-10-O-deacetyldaphylloside 89
10-O-p-Coumaroyl-10-O-deacetyl-11-demethoxy-11-ethoxydaphylloside 90
10-(E)-p-Coumaroyl-6,7-dihydromonotropein 45
10-(Z)-p-Coumaroyl-6,7-dihydromonotropein 46
6-O-E-p-Coumaroyl-3,4-dihydrocatalpol (Piscroside B) 25
6-O-(E)-p-Coumaroyl-8-epi-loganic acid 44
10-O-(E)-p-Coumaroylscandoside 47
10-O-(Z)-p-Coumaroylscandoside 48
6-O-p-Coumaroyl-8-epikingiside 126
6-O-E-p-Coumaroylgardoside 72
4-O-[(E)-p-Coumaroyl]-gentiobiosylgenipin 82
6-O-Cyclopropanoyltheviridoside 79
Daphmacropodosidine A 122
Daphmacropodosidine B 123
6,7-Dehydro-8-acetylharpagide 9
5-Dehydro-8-epi-adoxosidic acid 56
7,8-Dehydroharpagide 3
5-Dehydro-8-epi-mussaenoside 110
11-Demethoxy-11-ethoxydaphylloside 93
7-Deoxyloganic acid-b -D-glucopyranosyl ester 96
8-Deoxyshanzhiside 69
6,8-Diacetylharpagide 16
6,8-Diacetylharpagide-1-O-b -(2,3-di-O-acetylglucoside) 17
1,5-Dihydroxy-3,8-epoxyvalechlorine A 152
10-O-Dihydroferuloyl-10-O-deacetyldaphylloside 94
Dipsanoside A 171
Dipsanoside B 172
Dipsanoside C 163
Dipsanoside D 164
Dipsanoside E 165
Dipsanoside F 166
Dipsanoside G 167
Eucomoside A 95
Eucomoside B 84
Eucomoside C 85
6-epi-Barlerin 108
13(R)-epi-Epoxygaertneroside 119
13(R)-epi-Gaertneroside 118
Eriobioside (Ipolamiide 6-O-b -glucopyranoside) 111
6-O-Feruloylharpagide 12
6-O-a -D-Galactopyranosylbarlerin 107
6-O-a -D-Galactopyranosylphlorigidoside C 103
6-O-a -D-Galactopyranosylshanzhiside methyl ester 109
6-O-a -D-Galactopyranosylsesamoside 105
Gardaloside 43
Genameside A 73
Genameside B 74
Genameside C 75
Genameside D 76
Genestifolioside 15
Genipin-1-O-a -L-rhamnopyranosyl(16)-b -D-glucopyranoside 78
Globularioside 1
6-O-b -D-Glucopyranosylbarlerin 106
6-O-Glucopyranosylharpagoside 13
5-O-b -Glucopyranosylharpagide 14
6-O-b -D-Glucopyranosylphlorigidoside C 102
6-O-b -Glucopyranosylsecologanoside 131
6-O-b -D-Glucopyranosylsecologanol 132
6-O-b -D-Glucopyranosylsesamoside 104
3-O-b -D-Glucopyranosylsweroside 130
Harpagide 6-O-b -glucoside 7
Harprocumbide A (6-O-a -D-Galactopyranosyl-harpagoside) 18
Harprocumbide B (6-O-(cis-p-Coumaroylprocumbide)) 6
Hedycoryside A 83
Hedycoryside B 86
Hedycoryside C 51
6-O-p-Hydroxybenzoylantirrinoside 5
2-O-(3-Hydroxybenzoyl)-8-epikingiside 124
2-O-(3-Hydroxybenzoyl)-kingiside 125
10-O-p-Hydroxybenzoyltheveridoside 80
6b -Hydroxy-7-epigardoside methyl ester 114
6b -Hydroxy-2-oxabicyclo[4.3.0]non-8-en-1-one 147
Incaside 170
Isoplumericin 150
10-Isovalerylkanokoside C 117
Kankanol 141
Kankanoside A 42
Kankanoside B 33
Kankanoside C 34
Kankanoside D 129
6-Keto-8-acetylharpagide 10
Lamalbidic acid 70
Lamerioside 112
Loganic acid 11-O-b -glucopyranosyl ester 97
Marinoid A 64
Marinoid B 65
Marinoid C 66
Marinoid D 54
Marinoid E 55
2-O-(4-Methoxycinnamoyl)mussaenosidic acid 68
8-Methylvalepotriate 154
Morindacin 140
Myobontioside A 36
Myobontioside B 31
Myopochlorin 143
Paederoside B 168
Pensteminoside 27
1b ,6b ,7a ,8a ,10-Pentahydroxy-cis-2-oxabicyclo[4.3.0]nonane 146
2-O-[(2E,4E)-5-Phenylpenta-2,4-dienoyl]mussaenosidic acid 67
Picroroside A 38
Picroroside B 39
Picroroside C 40
Piscrocin D 142
Piscrocin E 137
Piscrocin F 138
Piscrocin G 139
Piscroside A (7-Deoxy-7-a -Cl-pikuroside) 37
Piscroside B (6-O-E-Cinnamoyl-3b -methoxy-3,4-dihydro-catalpol) 26
Plumericin 149
Prismatomerin 151
Rupesin A 159
Rupesin B 162
Rupesin C 160
Rupesin D 161
Rupesin E 153
Scutelloside 41
Scyphiphorin A (10-O-Benzoylgeniposidic acid) 52
Scyphiphorin B 53
Shanzhilactone 136
6-O-[(E)-Sinapoyl]gardoside 71
August 2009
793
6-O-Sinapoylgeniposide 77
Stachysoside E (3-O-p-Coumaroyl ester of melittoside) 20
Stachysoside F 21
Stachysoside G 22
Stachysoside H 23
Stereospermoside (6-O-trans-p-Coumaroyl-decinnamoyl globularimin) 35
Tarennin (artifact) 148
Tarenninoside A 57
Tarenninoside B 58
Tarenninoside C 59
Tarenninoside D 60
Tarenninoside E 61
Tarenninoside F 62
Tarenninoside G 63
Teneoside A (10-O-(a -L-Rhamno) deacetylasperuloside) 98
Teneoside B 87
6b ,7b ,8a ,10-Tetrahydroxy-cis-2-oxabicyclo[4.3.0]nonan-3-one 144
6b ,7b ,8a ,10-Tetra-p-hydroxybenzoyl-cis-2-oxabicyclo[4.3.0]nonan-3-one

145
Tudoside 113
(E)-Uenfoside 120
(Z)-Uenfoside 121
Valeriotetrate C 156
Valeriotriate A 157
Valeriotriate B 158
10-O-Vanilloyltheviridoside 81
6-O-Vanilloyl-3,4-dihydrocatalpol (Piscroside A) 24
Verbenabraside A 127
Verbenabraside B 128
Versibirioside 32
Viburtinoside A 115
Viburtinoside B 116
Wendoside 101
Fig. 2
hypertensive drugs formulations. This fact encouraged for

extensive study of different bioactivities of the isolated iridoids, secoiridoids and other phytochemicals from these
plant extracts. The biological study on this class of compounds revealed that these compounds exhibit a wide range
of bioactivity. In the present review only the pharmacological
or biological activities of pure iridoids and secoiridoids published during mid 2005 to 2008 are highlighted.
a. Antibacterial Activity The roots of Patrinia rupestris have long been used as Chinese folk medicine for
treatment of enteritis, appendicitis and hepatitis.74) To find
out the bioactive principles from the root of this plant, Yang
et al. isolated several iridoids and evaluated their antibacterial activities. Out of them, two iridoids namely, rupesins
C (160) and D (161) showed significant antibacterial activities against Bacillus subtilis, Escherichia coli and Staphylo-
coccus aureus at a concentration of 100 m g/ml with inhibition zones of 1320 mm in diameter in cup-plate assay
method.68)
b. Antifungal Activity Iridoid glycoside, 6b -hydroxy7-epigardoside methyl ester (114) isolated from Brazilian
Rubiaceae plant, Alibertia edulis showed moderate antifungal activity against Candida albicans and C. krusei with an
MIC value of 125 m g/ml in a dilution assay method.54)
c. Anticancer Activity The leaves of evergreen shrub,
Prismatomeris tetrandra of temperate areas of Bangladesh
and ajoining areas of India have been used in treatment of
several ailments like stomachaches and poultices of fresh
wounds.75) Phytochemical investigation afforded several iridoids. Among the isolated iridoids, prismatomerin (151)
showed remarkable antitumor activity against four mammalian cancer cell lines. L-929 (murine connective tissue),
794
KB-3-1 (human cervix carcinoma), A-549 (human lung carcinoma) and SW-480 (human colon adenocarcinoma) with
IC50 values of 0.21, 0.41, 1.41 and 0.06 m M, respectively in in
vitro sulforhodamine B (SRB) protein assay method.66) This
compound also showed cell killing effect in solid tumor cell
lines like renal cancer (A 498), prostrate cancer (PC-3) and
breast cancer (MCF 7) with LC50 values in the range of 100
to 0.6 m M.66)
Morroniside (173) a C10-iridoid glucoside isolated from
Lonicera spp. prevented significantly hydrogen peroxide
(H2O2) induced apoptosis in human neuroblastoma SHSY5Y cells at a concentration of 1100 m M by elevation of
cellular glutathione (GSH) levels.76)
Aucubin (174) isolated from the leaves of Aucuba japonica inhibited human lung cancer (A-549) cell line by blocking the cell cycle progression in the G(0)/G(1) phase and inducing apoptosis. An enzyme linked imnunosorbent (ELISA)
assay showed that the G(0)/G(1) phase arrest was possibly
due to p53-mediated induction of p21.77)
8-O-(p-Coumaroyl)-harpagide (175) of Harpagophytum
procumbens showed moderate inhibition activity against respiratory raw 264.7 macrophage cell line with an IC50 value of
about 32 m M in chemiluminescence assay method. Phorbol
12-myristate 13-acetate (PMA) was applied as triggering
agent and chemiluminescence was measured with luminal.11)
It may be noted that the dried tubers of the plant are traditionally used as a folk medicine for treatment of skin cancer,
allergics, rheumatism and arthritis.78)
d. Anticardiac Activity The roots of Scrophularia
ningpoensis have been used as a famous herbal medicine in
China for the treatment of hypertension, inflammation, dry
cough, pharyngitis and pulmonary tuberculosis.79) From the
60% ethanol extract of the roots of this plant several iridoid
and aromatic glycosides have been isolated and their activity
on the regulation of Ca2 ion concentration on rat cardiac
myocytes was evaluated. It was observed that iridoid glycosides (11, 176, 177) significantly inhibited the increase of
Ca2 ion induced by KCl at 100 m M. This study indicates that
these iridoids might contribute to prophylactic and therapeutic effects on myocardial damage through accumulation of
Ca2 ions.12)
e. Anti-coagulant Activity The iridoid diglycoside
(78) isolated from the bark of Adina polycephala showed potent in vitro inhibitory activity against the release of b -glucuronidase in rat polymorphonuclear leukocytes induced by
platelet-activating factor (PAF) with an inhibitory rate of
44.8% at a concentration of 105 M. At the same concentration, the positive control, ginkgolide B gave an inhibition rate
of 78.8%. Hence the use of this plant in treatment of inflammatory diseases is justified.43)
f. Anti-inflammatory Activity The anti-inflammatory
potency of seven iridoid glucosides namely, aucubin (174),
catalpol (178), gentiopicroside (179), swertiamarin (180),
geniposide (181), geniposidic acid (182) and loganin (183)
was investigated with in-vitro testing model systems on inhibition of cyclooxygenase (COX)-1/2 enzymes, the tumor
necrosis factor (TNF-a ) formation and nitric oxide (NO)
production. No single iridoid glucoside exhibited any activities. b -Glucosidase hydrolysis product of the iridoids showed
inhibitory activities of different potenties, depending on their
chemical structures. The hydrolysed (H)-geniposide and H-
Vol. 57, No. 8
loganin exhibited high inhibitory potencies on COX-1 with

IC50 values of 3.55 and 5.37 m M, respectively. The H-aucubin
showed a moderate inhibition on COX-2 with IC50 of
8.83 m M but much less inhibition on COX-1 (IC50, 68.9 m M).
In addition, H-aucubin only exhibited suppressive activities
on both NO production and TNF-a formation with IC50 values of 14.1 and 11.2 m M, respectively. Genipin, an aglycone
form showed no inhibitory effects on all the testing models,
suggesting that possibly the enzymatic hydrolysis of the glycosidic bond of iridoid glycoside is a pre-requisite step to
produce various biological activities.80)
The Brazilian popular tree, Tabebuia avellanedae is used
as anti-inflammatory medicine in Latin America. Its water
extract of the inner bark showed inhibitory activity on NO
production in lipopolysaccharide (LPS)-activated J 774.1
macrophage-like cells with an IC50 value of 64.7 m g/ml. To
find out the bioactive principle from the water extract, fifteen
compounds were isolated. Among the isolated compounds,
four iridoids (134, 184186) showed potent NO inhibitory
activity (IC50 values in the range of 13.826.1 m g/ml) compared to that of the positive control NG-monomethyl-L-arginine (L NMMA; IC50, 27.4 m g/ml).60) This result corroborated the traditional use of this plant as an anti-inflammatory
medicine.
g. Antioxidative Activity Secoiridoid, verbenabraside
A (127) isolated from Japanese wild plant, Verbena
brasiliensis exhibited stronger radical scavenging effect on
1,1-diphenyl-2-picrylhydrazyl (DPPH) radical than that of
standard antioxidant, a -tocopherol at the same concentration
of 0.02 mM in 0.1 M acetic acid buffer (pH 5.5) solution in
spectrophotometric assay at 517 nm.57)
Iridoid, ajugoside C (187) isolated from Sideritis perfoliata L. subsp. perfoliata of Greek origin exhibited weak antioxidative effect on DPPH radical in the range of 6.3
23.6% at a concentration of 0.1 m M in spectrophotometric
assay method.81)
h. Anti-protozoal Activity Iridoids, epoxygaertneroside (188), methoxygaertneroside (189), gaertneroside (190),
acetylgaertneroside (191) and gaertneric acid (192) isolated
from 80% methanolic extract of Morinda morindoides leaves
showed significant antiamoebic activity against Entamoeba
histolytica with IC50 values of 1.3, 2.3, 4.3, 5.4 and 7.1 m g/
ml, respectively. All these iridoids were devoid of any cytotoxic effect against MT-4 cells at the highest test concentration of 250 m g/ml.82)
i. Hepatoprotective Activity The Chinese plant, Neopicrorhiza scrophulariiflora is used in traditional Chinese medicine for treatment of damp-heat dysentery, jaundice and
steaming of bone.83) The ethanol extract of this plant had
been shown to possess hepatoprotective activities against carbon tetrachloride (CCl4), thioacetamide and acetaminopheninduced liver damage in mice.84) Bioassay guided analysis of
n-BuOH portion from the ethanol extract of this plant led to
the isolation of thirteen non-glycosidic iridoids and iridoid
glycosides. Study of the hepatoprotective activity of these iridoids on CCl4-induced mice hepatocytes damage in vitro indicated that piscroside B (26), picroside II (193), picroside I
(194), and picroside III (195) exhibited potent hepatoprotective effects with IC50 values of 7.3, 4.7, 8.3 and 5.9 m M, respectively. It was also observed that iridoids with a glycosidic linkage at C-1 were less active than those non-glyco-
August 2009
sidic iridoids. These observations revealed that major iridoid

glycosides are probably the pro-drugs and those non-glycosidic iridoids derived from the parent compounds are the
pharmacophores.57)
j. Neuroprotective Activity Catalpol (178) contained
richly in the roots of Rehmannia glutinosa was found to be of
neuroprotection in Mongolian gerbils subjected to transient
global cerebral ischemia. Catalpol at a dose of 1 mg/kg body
wt intraperitoneally (i.p.) used immediately after reperfusion
and repeatedly at 12, 24, 48 and 72 h significantly rescued
neurons in hippocampal CA1 subfield and reduced working
errors during behavioral testing. The neuroprotective efficacy
of catalpol became more evident when the doses were increased to 5 and 10 mg/kg body weight. This neuroprotective
efficacy of catalpol became weak when catalpol was given at
6 h after ischemia. This neuroprotection of catalpol was seen
in a long post-ischemic period (35 d). All these findings indicated that catalpol might be of therapeutic value for the treatment of global cerebral ischemia.85)
Catalpol (178) also showed significant neuroprotective
efficacy in memory damage of mice induced by subcutaneous injection of d-galactose (150 mg/kg body weight) for
six weeks and application of catalpol in the dose range of
2.510 mg/kg body weight for the last two weeks. The brain
damage and pathological alternations were measured by
hematoxylin and eosin (HE) staining. It was observed that
the activities of glutathione S-transferase (GSH-ST), glutathione synthetase (GS) and creative kinase (CK) were decreased while the activity of lactate dehydrogenase (LDH)
was increased in aging mice brain cortex. This result indicates that catalpol might be useful for the study of neurodegenerative diseases such as Alzheimers disease and Parkinsons disease.86)
Catalpol also exhibited neuroprotective effect on 1-methyl4-phenylpyridinium (MPP)-induced oxidative stress in cultured mesencephalic neurons especially dopaminergic neurons in a dose-dependent manner.87)
Catalpol also protected the H2O2-injured astrocytes which
have critical role in the brain for neurodegenerative disorders. Possibly this iridoid protected them by reducing intracellular ROS formation.88)
(E)-Harpagoside (177) and 8-O-(E)-p-methoxycinnamoyl
harpagide (196) isolated from Scrophularia buergeriana
exerted potent cognitive-enhancing activity in scopolamine
induced amnestic mice at a dose of 2 mg/kg body weight,
per os (p.o.). Donepezil, an acetylcholinesterase inhibitor and
most widely used drug for Alzheimers disease treatment was
employed as positive control. The activity of acetylcholinesterase was inhibited significantly by both (E)-harpagoside
and 8-O-(E)-p-methoxycinnamoyl harpagide (MCA-Hg)
within the cortex and hippocampus to a level similar to that
observed in mice treated with donepezil (2 mg/kg body
weight, p.o.). The treatment with (E)-harpagoside or MCAHg to scopolamine-induced amnestic mice also significantly
decreased TBARS level. Thus this cognitive-enhancing activity of the iridoids was possibly took place through both antiacetylcholinesterase and anti-oxidant mechanisms.89)
k. Antinociceptive Activity Monotropein (197) isolated from the roots of Morinda officinalis significantly contributed to antinociceptive activity by reducing streching
episodes in mice in hot plate and writhing assays at a dose of
795
20 and 30 mg/kg body weight p.o.90)

Acknowledgements Preparation of this manuscript was financially supported by UGC, New Delhi (Grants No. 31-127/2005). The authors thank
Dr. Braja Gopal Samanta, Hiroshima University, Japan; Dr. Subhendu Das,
University of Iowa, U.S.A.; Dr. Mohitlal Deb, IISc, Bangalore; Dr. Subhajit
Dinda, Jadavpur University and Dr. Saikat Das Sarma, RRL, Jorhat for their
help in collection of some papers.
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Iridoides DINDA

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Chem. Pharm. Bull.

57(8) 765796 (2009)

iridoid; secoiridoid; physical data; spectral data; plant source; bioactivity

atoms of C, H, O, N, S, etc.; melting point (C) of crystalline

2009 Pharmaceutical Society of Japan

Vol. 57, No. 8

List of New Iridoids

Group 2b (9-Carbon skeleton; ninth carbon on C-8)

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Scyphiphorin A (10-O-Benzoylgeniposidic acid)

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7-Deoxyloganic acid-b -D-glucopyranosyl ester

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6-O-a -D-Galactopyranosylshanzhiside methyl ester

Eriobioside (Ipolamiide 6-O-b -glucopyranoside)

6b -Hydroxy-7-epigardoside methyl ester

Group 3b (Iridoid glycosides with 10-carbon skeleton, valeriana type)

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Group 3d (Rearranged iridoid glycosides: with 10-carbon skeleton)

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Group 5 (Iridoid aglycones and derivatives)

6b ,7b ,8a ,10-Tetrahydroxy-cis-2-oxabicyclo[4.3.0]nonan-3-one

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cally listed in Table 2.

Biological and Pharmacological Activity of Naturally Occurring Iridoids and Secoiridoids

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6b ,7b ,8a ,10-Tetra-p-hydroxybenzoyl-cis-2-oxabicyclo[4.3.0]nonan-3-one

hypertensive drugs formulations. This fact encouraged for

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loganin exhibited high inhibitory potencies on COX-1 with

sidic iridoids. These observations revealed that major iridoid

20 and 30 mg/kg body weight p.o.90)

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