Electronic Supplementary Information www.rsc.org/greenchem | Green Chemistry | p.

DOI: 10.1039/b605138c

A green catalyst for green chemistry: Synthesis and application of an

olefin metathesis catalyst bearing a quaternary ammonium group

Anna Michrowska,a Łukasz Gułajski,a,b Zuzanna Kaczmarska,a,c Klaas Mennecke,d

Andreas Kirschningd and Karol Grelaa, *

a
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01–224
Warsaw, Poland. b Faculty of Chemistry, Warsaw University of Technology (Politechnika),
Noakowskiego 3, 00–664, Warsaw, Poland. c Department of Chemistry, Warsaw University,
Pasteura 1, 02–093 Warsaw, Poland. d Institut für Organische Chemie, Universität Hannover,
Schneiderberg 1b, 30167 Hannover; Germany

E-mail: [email protected]
WWW: http://zinc.icho.edu.pl/

Contents

1. General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2. Preparation of catalysts 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. N,N-diethyl-N-3-isopropoxy-4-[(E,Z)-1-propenyl]-phenylamine (10) . . . . . . . . . . . . . . . 2
2.2. Diethyl(methyl)[3-izopropoxy-4-[(E/Z)-prop-1-en-1-yl]phenyl]ammonium iodide (11) . . . . . . 3
2.3. Quaternary salt 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3. General procedures for metathesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3.1. Representative procedure of metathesis in CH2 Cl2 . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2. Representative procedure of metathesis in EtOH–H2 O and MeOH–H2 O . . . . . . . . . . . . . 4

4. General procedure for residual ruthenium analyses . . . . . . . . . . . . . . . . . . . . . . . . . . 5

5. Analytical data of isolated products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

Created: 8th June 2006 with: LATEX 2ǫ (pdfTeX (Web2C 7.3.1) 3.14159-0.14f-released-20000525 Linux) DOI: 10.1039/b605138c
Electronic Supplementary Information www.rsc.org/greenchem | Green Chemistry | p. 2

1. General

Unless otherwise noted, all reactions were carried out under Ar in the “Radleys Heated Carousel
Reaction Station” parallel reactor (www.radleys.com). The solvents were dried by distillation over
the following drying agents and were transferred under argon: THF (K/benzophenone), toluene (Na),
n-pentane, n-hexane, CH2 Cl2 (CaH2 ), Et2 O (LiAlH4 ), MeOH (Mg). Flash column chromatography:
Merck silica gel 60 (230–400 mesh). NMR: Spectra were recorded on Bruker AVANCE 500, Varian
Gemini 200 and 400 spectrometers in CDCl 3 ; chemical shifts (δ) are given in ppm relative to TMS,
coupling constants (J) in Hz. IR: Perkin-Elmer Spectrum 2000 FT-IR, wavenumbers in cm −1 . MS
(EI, LSIMS): AMD 604 Intectra GmbH. MS (ESI): Mariner Perseptive Biosystems, Inc. GC: HP
6890 with HP 5 column. GC/MS: HP 5890 with HP 5 column. Micro-analyses were provided by
Institute of Organic Chemistry, PAS, Warsaw. 4-(Diethylamino)-2-hydroxybenzaldehyde (9), methyl
iodide, 2-propyl iodide, CuCl and carbene 1b were purchased from Aldrich.

2. Preparation of catalysts 8

2.1. N,N-diethyl-N-3-isopropoxy-4-[(E,Z)-1-propenyl]-phenylamine (10)

K2 CO3 (1.24 g, 9.0 mmol) and Cs2 CO3 (410 mg, 1.26 mmol ) were placed in a round bottom
flask. A solution of 4-(diethylamino)-2-hydroxybenzaldehyde 9 (1.16 g, 6.0 mmol) in dry DMF (15
mL) was added. After stirring for 10 minutes at room temperature 2-iodopropane (0.9 mL, 9.0 mmol)
was added. The reaction was carried out for the next 24 hours at room temperature. After pouring onto
a saturated aqueous solution of K 2 CO3 the reaction mixture was extracted with MTBE. The combined
organic layers were washed with 1M solution of NaOH and then with brine, dried (MgSO 4 ) and the
solvent was removed under reduced pressure. Crude 4-(diethylamino)-2-isopropoxybenzaldehyde was
obtained as a dark red oil (1.28 g, 5.4 mmol; 91%). IR (film) ν/cm −1 2976, 2930, 2867, 2836, 2758,
1658, 1587, 1547, 1521, 1471, 1146, 1406, 1391, 1356, 1299, 1129, 1238, 1210, 1106, 1076, 1015,
979, 930,; 1 H NMR (200 MHz, C6 D6 ) δH /ppm: 10.72 (s, 1H), 8.10 (d, J = 9.2 Hz, 1H), 6.03 (dd,
J = 9.2, 2.1 Hz, 1H), 5.93 (d, J = 2.1 Hz, 1H), 4.30 (septet, J = 6.0 Hz, 1H), 2.87 (q, J = 7.1 Hz,
4H), 1.09 (d, J = 6.0 Hz, 6H), 0.82 (t, J = 7.1 Hz, 6H); 13 C NMR (50 MHz, C6 D6 ) δC /ppm: 186.4,
163.0, 153.6, 130.5, 116.6, 105.1, 95.7, 70.7, 44.6, 22.0, 12.6; MS (EI) m/z 235 (32) [M +· ], 220 (31),
192 (7),178 (100), 162 (9), 150 (14), 148 (8), 136 (2), 122 (4), 106 (2), 94 (4), 77 (5), 65 (9), 41 (9),
HRMS (EI) calcd. for C14 H21 O2 N: 235.1572 [M+· ]; found: 235.1580.
To a solution of dry THF (450 mL) and ethyltriphenylphosphonium bromide (22.08 g, 59.46 mmol)
under argon at −78 ◦ C was added dropwise n-BuLi (2.5 M in hexane 25.6 ml, 63.7 mmol). After 15
minutes at −78 ◦ C the solution was heated at 30 ◦ C for three hours. After this period the solution was
cooled again to −78 ◦ C and 4-(diethylamino)-2-isopropoxybenzaldehyde (10 g, 42.26 mmol) was added.
After 30 minutes the reaction mixture was warmed to room temperature and was stirred overnight at
this temperature. After pouring onto a saturated aqueous solution of NaHCO 3 the reaction mixture was
extracted with MTBE. The combined organic layers were dried (MgSO 4 ) and the solvent was removed
under reduced pressure. The crude product was purified by flash column chromatography (5% ethyl
acetate in hexane with 1.5% triethyl amine) to afford 10 as a yellow oil (10.3 g, 41.6 mmol, 98%;
(E)/(Z)= 2:1).
 Electronic Supplementary Information www.rsc.org/greenchem | Green Chemistry | p. 3

IR (film) ν/cm−1 3025, 2973, 2931, 1611, 1555, 1511, 1467, 1449, 1396, 1374,
1356, 1275, 1222, 1115, 1020, 969, isomer (E): 1 H NMR (400 MHz, CDCl3 )
δH /ppm: 1.19 (t, J = 7.0 Hz, 6H), 1.38 (d, J = 6.0 Hz, 6H), 1.89 (dd, J = 6.6, 1,7
O Hz, 3H), 3.36 (q, J = 7.0 Hz, 4H), 4.50 (heptet, J = 6.0 Hz, 1H), 6.03 (dq, J =
Et2N 17,8, 6,6 Hz, 1H), 6.26 (d, 2.5 Hz, 1H), 6.31–6.34 (m, 1H), 6.60 (dd, J = 17.8,
1,7 Hz, 1H), 7.33 (d, J = 11.0 Hz, 1H), isomer (Z): 1 H NMR (400 MHz, CDCl3 )
δH /ppm: 1.17 (t, J = 7.0 Hz, 6H), 1.35 (d, J = 6.0 Hz, 6H), 1.86 (dd, J = 7.1, 1.7
Hz, 3H), 3.34 (q, J = 7.0 Hz, 4H), 4.50 (heptet, J = 6.0 Hz, 1H), 5.63 (dq, J =
11.1, 7.1 Hz, 1H), 6.21 (d, J = 2.5 Hz, 1H), 6.25–6,30 (m, 1H), 6.54 (dq, J = 11.1,
1.7 Hz, 1H), 7.21 (d, J = 8.5 Hz, 1H), isomer (E): 13 C NMR (125 MHz, CDCl3 )
δC /ppm: 13.0, 15.2, 22.6, 44.8, 71.4, 99.8, 104.6, 116.9, 121.4, 125.6, 127.4, 148.2,
156.1, isomer (Z): 13 C NMR (125 MHz, CDCl3 ) δC /ppm: 13.0, 19.2, 44.8, 71.4,
99.7, 105.8, 116.2, 123.2, 126.2, 131.0, 148.2, 157.1, HRMS (ESI (+)): calcd for
[M+H]+ (C16 H25 NO): 248.1936. found 248.1939.a

a
Michrowska, A. PhD Thesis, Institute of Organic Chemistry, Polish Academy of Sciences, Warsaw,
Poland, 2006.

2.2. Diethyl(methyl)[3-izopropoxy-4-[(E/Z)-prop-1-en-1-yl]phenyl]ammonium iodide (11)

Amine 10 (0.074 g, 0.3 mmol) and neat MeI (0.23 mL, 3.6 mmol) were placed in a round bottom
flask and stirred at room temperature for 2 days. Excess of MeI was evaporated to dryness to give 11
(0.116 g, 0.3 mmol, 100 %) as a colourless solid ((E):(Z) = 4:1).
IR (film drom CH2 Cl2 ) ν/cm−1 3481, 2977, 2934, 1652, 1601, 1496, 1451, 1425,
1385, 1331, 1295, 1253, 1213, 1170, 1140, 1111, 1028, 973, 904, 881, isomer (E):
1 H NMR (400 MHz, CDCl ) δ /ppm: 1.14 (t, J= 7.1 Hz, 6H), 1.39 (d, J= 5.9 Hz,
3 H
O 6H), 1.93 (dd, J= 6.7, 1.7 Hz, 3H), 3.70 (s, 3H), 4.37–4.59 (m, 4H), 4.99 (heptet,
N J= 5.9 Hz, 1H), 6.34 (dq, J= 16.0, 6.7 Hz, 1H), 6.66 (dq, J= 16.0, 1.7 Hz, 1H),
I
7.05 (dd, J= 8.7, 2.6 Hz, 1H), 7.29 (d, J= 2.6 Hz, 1H), 7.53 (d, J= 8.7 Hz, 1H),
isomer (Z): 1 H NMR (400 MHz, CDCl3 ) δH /ppm: 1.14 (t, J= 7.1 Hz, 6H), 1.39
(d, J= 5.9 Hz, 6H), 1.84 (dd, J= 7.1, 1.8 Hz, 3H), 3.72 (s, 3H), 4.37–4.59 (m, 4H),
4.99 (heptet, J= 5.9 Hz, 1H), 5.92 (dq, J= 11.7, 7.1 Hz, 1H), 6.48 (dq, J= 11.7,
1.8 Hz, 1H), 7.09 (dd, J= 8.7, 2.6 Hz, 1H), 7.33 (d, J= 2.6 Hz, 1H), 7.43 (d, J=
8.7 Hz, 1H), isomer (Z): 13 C NMR (100 MHz, CDCl3 ) δC /ppm: 8.8, 19.0, 22.0,
46.3, 64.7, 72.0, 107.2, 113.0, 124.1, 127.4, 129.5, 130.5, 139.4, 156.0. MS (ESI
(+)) m/z 262.2 ([M−126]+ ), . HRMS (ESI (+)): calcd for [M−126]+ (C17 H28 NO):
262.2165. found 262.2162.a

a
Michrowska, A. PhD Thesis, Institute of Organic Chemistry, Polish Academy of Sciences, Warsaw,
Poland, 2006.
 Electronic Supplementary Information www.rsc.org/greenchem | Green Chemistry | p. 4

2.3. Quaternary salt 8

Carbene complex 1b (0.081 g, 0.10 mmol), CuCl (0.014 g, 0.14 mmol) and CH 2 Cl2 (3 mL) were
placed in a Schlenk flask equipped with a condenser. A solution of 11 (0.045 g, 0.11 mmol) in CH 2 Cl2
(3 mL) was then added and the resulted solution was stirred under argon at 40 ◦ C for 15 min. From
this point forth, all manipulations were carried out in air with reagent-grade solvents. The reaction
mixture was concentrated in vacuo and to the residue EtOAc (10 mL) was added. The solution was
filtered off and the residue was washed on a Buchner funnel with MeOH (20 mL) and dried under
vacuum to give complex 8 as green microcrystalline solid (0.051 g, 63 %).
IR (KBr) ν/cm−1 3431, 2928, 2852, 1629, 1592, 1484, 1448, 1430, 1398, 1384,
N N Mes 1295, 1262, 1214, 1168, 1141, 1098, 1030, 980, 898, 852, 821, 1 H NMR (500
Mes
Cl MHz, CDCl3 ) δH /ppm: 1.05 (br.s, 6H), 1.34–1.55 (m, 6H), 2.40 (s, 6H), 2.46 (s,
Ru
Cl 12H), 3.60 (s, 3H), 4.18 (s, 4H), 4.20–4.65 (m, 4H), 5.25–5.45 (m, 1H), 6.90–7.15
O (m, 6H), 7.60 (s, 1H), 16.59 (s, 1H), 13 C NMR (125 MHz, CDCl3 ) δC /ppm: 8.9,
N 19.4, 21.1, 22.0, 35.1, 51.5, 64.6, 78.3, 108.0, 115.7, 122.0, 126.8, 128.7, 129.4,
I 139.1, 139.5, 145.4, 153.5, 208.3, 290.1 HRMS (ESI (+)): calcd for [M−126] +
(C36 H50 N3 O35 Cl2 102 Ru): 712.23744. found 712.2379. a

a
Michrowska, A. PhD Thesis, Institute of Organic Chemistry, Polish Academy of Sciences, Warsaw,
Poland, 2006.

3. General procedures for metathesis

3.1. Representative procedure of metathesis in CH 2 Cl2

A reaction tube equipped with a magnetic stirring bar was charged with CH 2 Cl2 (10 mL), catalyst
8 (1–5 mol %) and substrate 12 (0.2 mmol). The reaction mixture was stirred at 25 ◦ C. After complete
conversion (TLC), the reaction mixture was passed through a cartridge containing silica gel (1–2 g).
The cartridge was washed with an additional portion of CH 2 Cl2 (10–20 mL). The CH2 Cl2 fraction
was concentrated under reduced pressure to yield crude product 13.

3.2. Representative procedure of metathesis in EtOH–H 2 O and MeOH–H2 O

A reaction tube equipped with a magnetic stirring bar was charged with catalyst 8 (6 mg, 0.007
mmol, 5 mol %) and non-degassed water (2 mL). To the resulting suspension a solution of substrate
12 (0.14 mmol) in MeOH or EtOH (5 mL) was added. The reaction mixture was stirred at 25 ◦ C.
After complete conversion (TLC), the reaction mixture was evaporated to dryness, dissolved in CH 2 Cl2
(5 mL) and passed through a cartridge containing silica gel (1–2 g). The cartridge was washed with
an additional portion of CH2 Cl2 (15–25 mL). The CH2 Cl2 fraction was concentrated under reduced
pressure to yield crude product 13.
Electronic Supplementary Information www.rsc.org/greenchem | Green Chemistry | p. 5

4. General procedure for residual ruthenium analyses

Samples of the crude metathesis product were digested with subboiled HNO 3 (4 mL) and H2 O2
(1 mL, p.a.; Merck), and diluted with dist. water (to 250 mL). The Ru determination was carried
out with an inductively coupled plasma mass spectrometer (ICP-MS) Thermo X7 ICP-MS (Thermo
Electron GmbH, Dreieich, Germany, www.thermo.com). This quadrupole instrument had a power of
1200W throughout the measurement. The gas flow rates were 1.0 ml/min (Nebuliser), 1.2 mL/min
(Auxiliary) and 13 mL/min (Cool) argon 4.8, respectively. Quantification was performed with liquid
Ru standards from 0.01–50µg/L. For drift corrections during the measurements a standard of 1µg/L
Ru was interspaced after every second sample measurement.

5. Analytical data of isolated products

CO2Et Diethyl 3-methylcyclopent-3-ene-1,1-dicarboxylate (13a)

CO2Et Colourless oil. IR (film) ν/cm
a −1 2982, 2937, 1733, 1446, 1367, 1252, 1184, 1161,
1
1097, 1022, 861, H NMR (500 MHz, CDCl3 ) δH /ppm: 1.24 (t, J= 7.0 Hz, 6H),
1.70 (d, J= 1.5 Hz, 3H), 2.93 (s, 2H), 2.96 (br.s, 2H), 4.19 (q, J= 7.0 Hz, 4H), 5.18
(d, J= 1.5 Hz, 1H), 13 C NMR (100 MHz, CDCl3 ) δC /ppm: 14.0 16.0, 40.8, 44.6,
59.4, 61.4, 121.2, 137.4, 172.3, , MS (EI) m/z 226 (24, [M] +· ), 181 (17), 180 (15),
153 (49), 152 (100), 136 (2), 134 (3), 125 (25), 124 (25), 107 (44), 97 (8), 93
(35), 81 (25), 80 (47), 79 (64), 77 (21), 67 (9), 55 (3), 53 (7), 39 (9), HRMS
(EI): calcd for [M]+· (C12 H18 O4 ): 226.1205. found 226.1210.

a
Taber, D. F.; Frankowski, K. J. J. Org. Chem. 2003, 68, 6047.

2,5-Dihydro-1-tosyl-1H-pyrrole (13b)
Colourless crystals,a IR (film) ν/cm−1 3048, 2910, 2854, 1928, 1595, 1492, 1476,
1450, 1336, 1305, 1288, 1161, 1103, 1070, 1017, 1001, 947, 819, 1 H NMR (200
O S O
MHz, CDCl3 ) δH /ppm: 2.42 (s, 3H), 4.12 (d, J= 4.5 Hz, 4H), 5.65 (d, J= 4.5
N Hz, 2H), 7.32 (d, J= 8.3 Hz, 2H), 7.72 (d, J= 8.3 Hz, 2H), 13 C NMR (50 MHz,
CDCl3 ) δC /ppm: 21.8 55.1, 125.7, 127.7, 130.0, 134.6, 143.7, MS (EI) m/z 223
(20, [M]+· ), 155 (25), 91 (100), 68 (80), 65 (52), 51 (12), 41 (44), 39 (52),

a
Fürstner, A.; Liebl, M.; Lehmann, C.; Piquet, M.; Kunz, R.; Bruneau, C.; Touchard, D.; Dixneuf,
P. H. Chem. Eur. J. 2000, 6, 1847.
Electronic Supplementary Information www.rsc.org/greenchem | Green Chemistry | p. 6

CO2Et Diethyl cyclopent-3-ene-1,1-dicarboxylate (13c)

CO2Et Colourless oil. IR (film) ν/cm
a −1 2983, 2934, 1733, 1642, 1446, 1367, 1256, 1182,

1073, 1017, 922, 1 H NMR (500 MHz, CDCl3 ) δH /ppm: 1.24 (t, J= 7.1 Hz, 6H),
3.01 (s, 4H), 4.19 (q, J= 7.1 Hz, 4H), 5.61 (s, 2H), 13 C NMR (125 MHz, CDCl3 )
δC /ppm: 14.1, 36.7, 61.2, 61.5, 127.8, 172.2, MS (EI) m/z 212 (43, [M] +· ), 199
(12), 195 (6), 173 (2), 167 (58), 166 (80), 153 (48), 149 (12), 139 (70), 138
(100), 127 (4), 125 (18), 111 (52), 110 (35), 94 (11), 93 (45), 83 (9), 79 (55),
67 (44), 66 (59), 65 (26), 55 (7),

a
Taber, D. F.; Frankowski, K. J. J. Org. Chem. 2003, 68, 6047.

1-[(4-Methylphenyl)sulfonyl]-2,3,6,7-tetrahydro-1H-azepine (13d)
Colourles solid.a IR (KBr) ν/cm−1 3030, 2942, 2899, 2855, 1657, 1596, 1450, 1332,
1286, 1162, 910, 816, 712, 1 H NMR (200 MHz, CDCl3 ) δH /ppm: 2.28 (m, 4H),
O S O
2.39 (s, 3H), 3.25 (m, 4H), 5.72 (m, 2H), 7.25 (d, J= 8.2 Hz, 2H), 7.64 (d, J=
N 8.2 Hz, 2H), 13 C NMR (50 MHz, CDCl3 ) δC /ppm: 21,5, 29,948,2, 126,9, 129,5,
130,1, 136,2, 142,9, MS (EI) m/z 251 (5, [M] +· ), 223 (2), 184 (6), 155 (4), 105
(2), 91 (19), 96 (16), 77 (1), 65 (13), 42 (100), HRMS (EI): calcd for [M] +·
(C13 H17 NO2 S): 251,0980. found 251,0979.

a
Grela, K.; Kim, M. Eur. J. Org. Chem. 2003, 963.

O Ph 2,2-Diphenyl-3-vinyl-2,5-dihydrofuran (13e)
Ph Colourless oil. IR (film) ν/cm
a −1 3427, 3059, 3026, 2925, 1765, 1682, 1598, 1490,

1447, 1226, 1179, 1064, 758, 700, 1 H NMR (500 MHz, CDCl3 ) δH /ppm: 4.11 (q,
J= 7.1 Hz, 1H), 5.10 (dd, J= 11.2, 0.8 Hz, 1H), 5.31 (dd, J= 17.7, 0.8 Hz, 1H),
6.16–6.18 (m, 1H), 6.20–6.27 (m, 1H), 7.10–7.40 (m, 10H), 13 C NMR (125 MHz,
CDCl3 ) δC /ppm: 60.3 94.5, 117.5, 124.8, 127.8, 127.9, 129.7, 143.3, 143.6, 171.1,
, MS (EI) m/z 248 (15, [M]+· ), 229 (8), 215 (9), 205 (18), 204 (12), 203 (19),
191 (13), 189 (10), 183 (15), 182 (22), 172 (11), 171 (77), 165 (17), 157 (18),
143 (15), 141 (10), 129 (10), 128 (22), 115 (23), 105 (100), 97 (14), 95 (9),
91 (34), 83 (11), 77 (43), 71 (16), 69 (15), 57 (20), 55 (14), 51 (14), 43 (41),
41 (12), 39 (9), HRMS (EI): calcd for [M]+· (C18 H16 O): 248,1201. found 248,1196.

a
Fürstner, A.; Ackermann, L.; Gabor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.
Thiel, O. R. Chem. Eur. J. 2001, 7, 3236.
 Electronic Supplementary Information www.rsc.org/greenchem | Green Chemistry | p. 7

O 1-Benzoyl-2,5-dihydro-1H-pyrrole (13f)
N Colourless oil.a IR (film) ν/cm−1 3480, 3061, 2862, 1638, 1616, 1575, 1447, 1418,
Ph
1355, 1198, 1000, 959, 908, 784, 1 H NMR (400 MHz, CDCl3 ) δH /ppm: 4.12–4.25
(m, 2H), 4.41–4.53 (m, 2H), 5.70–5.78 (m, 1H), 5.86–5.96 (m, 1H), 7.36–7.46 (m,
3H), 7.48–7.57 (m, 2H), 13 C NMR (100 MHz, CDCl3 ) δC /ppm: 53.3, 55.7, 125.1,
125.9, 126.7, 128.3, 129.8, 136.8, 169.8, MS (EI) m/z 173 (55, [M] +· ), 106 (9),
105 (100), 78 (4), 77 (43), 68 (7), 51 (12), 41 (5), 39 (5), HRMS (EI): calcd
for [M]+· (C11 H11 NO): 173.0840. found 173.0832.

a
Stille, J. K.; Becker, Y.J. Org. Chem. 1980, 45, 2139.

O (4Z)-8,9,10-trimethoxy-2,2-dimethyl-3,6-dihydro-2H-1,2-benzoxasilocine (13g)
Colourles oil.a IR (film) ν/cm−1 3397, 2957, 2937, 1602, 1494, 1464, 1416, 1304,
O 1277, 1253, 1198, 1161, 1096, 1045, 1022, 938, 907, 839, 798, 1 H NMR (400 MHz,
O O
Si CDCl3 ) δH /ppm: 0.20 (d, J= 3.1 Hz, 6H), 1.43–1.57 (m, 1H), 1.81–1.94 (m, 1H),
2.25–2.35 (m, 1H), 2.54–2.66 (m, 1H), 3.83 (s, 3H), 3.84 (s, 3H), 3.90 (s, 3H), 5.20
(dd, J= 9.3, 1.4 Hz, 1H), 5.62–5.73 (m, 1H), 5.85–5.96 (m, 1H), 6.61–6.72 (m, 1H),
7.20 (dd, J= 8.6, 0.5 Hz, 1H),13 C NMR (100 MHz, CDCl3 ) δC /ppm: −2.2, 18.5,
39.0, 56.0, 60.7, 60.9, 69.5, 107.2, 120.5, 126.9, 128.6, 131.6, 141.7, 149.9, 152.6,
MS (EI) m/z 308 (19, [M]+· ), 295 (7), 253 (5), 240 (17), 239 (100), 223 (26),
221 (6), 195 (7), 181 (5), 164 (6), 149 (5), 89 (13), 77 (4), 75 (7), 59 (7), 43
(2), 39 (2), HRMS (EI): calcd for [M]+· (C16 H24 O4 Si): 308,1444. found 308,1457.

a
Michrowska, A.; Gulajski, L.; Grela, K. Chem. Commun. 2006, 841.

1-[(4-Methylphenyl)sulfonyl]-3-vinyl-2,5-dihydro-1H-pyrrole (13h)
Colourless solida IR (KBr) ν/cm−1 2918, 2851, 1597, 1493,1450, 1342, 1305,
1162, 1100, 1017, 814, 669, 588, 548, 1 H NMR (200 MHz, CDCl3 ) δH /ppm:
N 2.43 (s, 3H), 4.15–4.23 (m, 4H), 5.04 (d, J= 17.7 Hz, 1H), 5.15 (d, J= 10.2
O S O
Hz, 1H), 5.64 (br.s, 1H), 6.35 (dd, J= 17.7, 10.2 Hz, 1H), 7.32 (d, J= 8.0 Hz,
2H), 7.73 (d, J= 8.2 Hz, 2H), 13 C NMR (50 MHz, CDCl3 ) δC /ppm: 21.9, 53.8,
55.4, 117.1, 123.7, 127.9, 130.2, 130.3, 134.6, 137.9, 143.9, MS (EI) m/z 249
(12, [M]+· ), 155 (6), 139 (2), 94 (100), 91 (40), 77 (2), 67 (27), 65 (20), 51 (2),

a
Fürstner, A.; Ackermann, L.; Gabor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.
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