J. Am. Chem. Soc., 1997, 119(29), 6949-6950, DOI:10.

1021/ja971400y

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C1997 American Chemical Society J. Am. Chem. Soc. V 119 Page6949 Lopez Supplemental Page 1

JAT1 7 C!
Bu 3 SnH-Catalyzed Barton-McCombie Deoxygenation of Alcohols

Rosa M. Lopez, David S. Hays, and Gregory C. Fu*

Department of Chemistry
Massachusetts Institute of Technology
Cambridge, MA 02139

SUPPORTING INFORMATION

I. General

Solvents were distilled from the indicated drying agents: benzene

(sodium /benzophenone); THF (sodium /benzophenone); CH 2 Cl 2 (calcium hydride);

Et 2 0 (sodium/benzophenone); toluene (molten sodium).

Anhydrous n-butanol and pyridine were purchased from Aldrich. Bu 3 SnH,

(Bu 3 Sn) 2 0, and PMHS dimer (1,3-bis(trimethylsiloxy)-1,3-dimethyldisiloxane) were

distilled prior to use. PMHS was degassed under vacuum. Other reagents were used

as received.

Analytical thin layer chromatography was performed using EM Reagents 0.25

mm silica gel 60 plates, and visualization was accomplished with potassium

permanganate, ethanolic phosphomolybdic acid, or 5% H 2 SO 4 /EtOH. Flash

chromatography was performed on EM Reagents silica gel 60 (230-400 mesh).

1H (300 MHz), 13C (75 MHz), and 1 1 9 Sn (112 MHz) nuclear magnetic resonance

spectra were recorded on a Varian XL-300 or a Varian Unity 300 NMR spectrometer

at ambient temperature. 1H data are reported as follows: chemical shift in parts per

million downfield from SiMe 4 (8 scale), multiplicity (br = broad, s = singlet, d =

doublet, t = triplet, q = quartet, and m = multiplet), coupling constant (Hz), and

integration. 13C chemical shifts are reported in ppm downfield from SiMe 4 (8 scale).
13C 1 19 Sn chemical
All spectra were determined with complete proton decoupling.

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C1997 American Chemical Society J. Am. Chem. Soc. V 119 Page6949 Lopez Supplemental Page 2

I. General

shifts are reported in ppm downfield from SnMe 4 (external, neat). All 119 Sn spectra

were obtained with complete proton decoupling.

Gas chromatographic analysis was carried out on a Hewlett Packard 5890 Series II

instrument using a DB-1 capillary column (J & W Scientific; 30 m length, 0.25 mm

inner diameter, 45.5 cm/min helium flow rate).

Infrared spectra were obtained on a Perkin-Elmer Series 1600 FT-IR

spectrophotometer (cm-1). High resolution mass spectra were recorded on a

Finnegan MAT System 8200 spectrometer. Melting points were obtained on

Thomas Hoover Unimelt capillary melting point apparatus.

All reactions were carried out under an atmosphere of nitrogen or argon in

oven-dried glassware with magnetic stirring, unless otherwise indicated.

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C1997 American Chemical Society J. Am. Chem. Soc. V 119 Page6949 Lopez Supplemental Page 3

II. Preparation of Thionocarbonate Derivatives

General Procedure.1 The alcohol was placed in a 100 mL round-bottom flask and
azeotropically dried (typically, 50 mL of toluene were evaporated at reduced
pressure). Phenyl chlorothionoformate (1.1 equiv) and pyridine (1.2 equiv) were
then added at 0 oC to a solution of the substrate in CH 2 Cl 2 (50 mL). The mixture was
allowed to stir at room temperature for the specified time, and then it was diluted
with CH 2 0C2 (50 mL) and washed with 2 N HC (2 x 75 mL) and water (2 x 75 mL).
The organic layer was dried and concentrated, and the resulting product was
purified by flash chromatography.
O-Cyclododecyl-O-phenylthionocarbonate (Table 1, entry 1). The general
procedure was followed using cyclododecanol (5.16 g, 28.0 mmol; reaction time: 1 h).
Purification by flash chromatography (hexanes/EtOAc, 20/1) afforded 8.29 g (92%) of
the desired product. 1H NMR (CDCl3 ): 8 7.45-7.37 (m, 2H), 7.32-7.27 (m, 1H), 7.13-7.10
(m, 2H), 5.56-5.48 (m, 1H), 1.91-1.68 (m, 4H), 1.55-1.30 (m, 18H); 13 C NMR (CDCl 3 ): 5
194.5, 153.3, 129.4, 126.4, 122.1, 84.0, 28.8, 24.2, 23.9, 23.7, 23.5, 21.2. The spectroscopic
data are consistent with the literature data. 1
1,2-Diphenyl-2-methoxy-1-O-(phenoxythiocarbonyl)ethane (Table 1, entry 2). The
general procedure was followed using -methoxy-a-phenylphenethyl alcohol (3.00
g, 13.0 mmol; 3 : 1 mixture of diastereomers; reaction time: 1.5 h). Purification by
flash chromatography (hexanes/EtOAc, 20/1) afforded 4.50 g (85%) of a 3: 1 mixture
of the desired products as a colorless oil. 1H NMR (CDCl3 ): (both isomers) 8 7.60-6.92
(m, 15H); major isomer 8 6.39 (d, J = 5.5, 1H), 4.69 (d, J = 5.5, 1H), 3.28 (s, 3H); minor
isomer 8 6.37 (d, J = 7.5, 1H), 4.62 (d, J = 7.5, 1H), 3.34 (s, 3H); 13C NMIR (CDCl 3 ): major
isomer 8 193.8, 153.4, 137.0, 135.4, 129.5, 128.5, 128.3, 128.2, 128.1, 128.0, 126.5, 121.9,

(1) Barton, D. H. R.; Dorchak, J.; Jaszberenyi, J. C. Tetrahedron 1992, 48, 7435-7446.

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C1997 American Chemical Society J. Am. Chem. Soc. V 119 Page6949 Lopez Supplemental Page 4

II. Preparation of Thionocarbonate Derivatives

87.5, 85.0, 57.4; minor isomer 6 194.2, 153.5, 136.8, 135.6, 122.0, 88.2, 85.8, 57.3 (other
resonances of the minor isomer are obscured); IR (neat): 1492, 1274, 1198, 1116, 699;
Anal. Calcd for C22 H 20 0 3 S: C, 72.50; H, 5.53. Found: C, 72.55; H, 5.70.
2,3;5,6-Di-O-isopropylidene-1-O-phenoxythiocarbonyl-a-D-mannofuranoside
(Table 1, entry 3). The general procedure was followed using 2,3;4,5-di-O-
isopropylidenemannose (2.00 g, 7.70 mmol; reaction time: 14 h). Purification by
flash chromatography (hexanes/EtOAc, 8/1) and then recrystallization from EtOH
afforded 1.80 g (59%) of the desired product. 1H NMR (CDCl 3 ): 8 7.39 (m, 2H), 7.27
(m, 1H), 7.18 (m, 2H), 5.92 (s, 1H), 5.88 (m, 2H), 4.45 (m, 1H), 4.09 (m, 2H), 3.98 (dd, J =
8.0, 3.3, 1H), 1.52 (s, 3H), 1.48 (s, 3H), 1.39 (s, 3H), 1.36 (s, 3H); 13C NMR (CDCl3 ): 8
167.4, 151.2, 129.7, 126.6, 121.4, 113.7, 109.7, 90.3, 86.3, 82.4, 79.8, 72.8, 67.1, 27.2, 26.2,
25.3, 24.9; IR (KBr): 2992, 2938, 2881, 1742, 1590, 1491, 1456, 1374, 1303, 1216, 1178, 1162,
1117, 1066, 835, 736, 688, 662, 516; mp: 100-102 'C; HRMS (FAB, m/e) calcd for
C 19 H 24 0 7 S (M+H) 397.1312; found 397.1318.
1,2;5,6-Di-O-isopropylidene-3-O-phenoxythiocarbonyl-a-D-glucofuranoside
(Table 1, entry 4). The general procedure was followed using 1,2;5,6-di-O-
isopropylideneglucose (4.00 g, 15.0 mmol; reaction time: 18 h). Purification by flash
chromatography (hexanes/EtOAc, 13/1) afforded 5.50 g (90%) of the desired product.
1H NMR (CDCl3 ): 8 7.44 (t, J = 7.3, 2H), 7.32 (t, J = 7.9, 1H), 7.10 (d, J = 8.0, 2H), 5.97 (d, J
= 3.7, 1H), 5.64 (d, J = 1.7, 1H), 4.80 (d, J = 4.2, 1H), 4.32 (m, 2H), 4.13-4.08 (m, 2H), 1.56
13 C NMR (CDCl 3 ): 8 193.8, 153.4, 129.7,
(s, 3H), 1.46 (s, 3H), 1.38 (s, 3H), 1.36 (s, 3H);
126.9, 121.9, 112.6, 109.6, 105.1, 85.2, 83.0, 79.8, 72.4, 67.2, 27.0, 26.8, 26.4, 25.4. The
spectroscopic data are consistent with the literature data.2

(2) Robins, M. J.; Wilson, J. S.; Hansske, F. J. Am. Chem. Soc. 1983, 105, 4059-4065.

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II. Preparation of Thionocarbonate Derivatives

5-Isopropenyl-2-methyl-2,3-oxy-1-O-phenoxythiocarbonylcyclohexane (Table 1,
entry 5). A 30% H 2 0 2 solution (22.4 g, 198 mmol) was added to a solution of (-)-
carvone (10.0 g, 66.0 mmol) in MeOH (60 mL). The reaction mixture was cooled to
-15 oC, and then a 6 N NaOH solution (5.50 mL, 33.0 mmol) was added. The reaction
was stirred at 0 oC for 4 h, and then it was diluted with water (50 mL) and extracted
with Et 2 0 (2 x 100 mL). The organic layers were combined, washed twice with water,
dried, and concentrated, to afford (-)-carvone oxide (7.32 g, 44.1 mmol) as a single
diastereomer. 3
NaBH 4 (1.70 g, 1.0 equiv) was added to a 0 oC solution of the unpurified epoxide

in MeOH (50 mL). The reaction mixture was stirred at 0 oC for 3 h and then at r.t.

overnight. The solvent was evaporated, and the residue was partitioned between
water and EtOAc. The organic layer was dried and then concentrated to afford 6.40 g
(38.0 mmol) of a 2 : 1 mixture of epimeric alcohols. 4
The general procedure for derivatization was followed, using the unpurified
mixture of alcohols (6.40 g, 38.0 mmol; reaction time: 16 h). The products were
purified and separated by flash chromatography (hexanes/EtOAc, 95/5), affording
3.10 g (15% from (-)-carvone) of one of the diastereomers. 1H NMR (CDCl 3 ): 8 7.43 (t,
J = 7.7, 2H), 7.30 (t, J = 7.5, 1H), 7.13 (d, J = 8.1, 2H), 5.69 (t, J = 5.7, 1H), 4.86 (s, 1H), 4.72
(s, 1H), 3.23 (s, 1H), 2.46-2.42 (m, 1H), 2.18 (dd, J = 15.0, 5.0, 1H), 1.94-1.85 (m, 3H), 1.79
(s, 3H), 1.45 (s, 3H); 13C NMR (CDC13 ): 8 195.4, 153.6, 147.1, 129.6, 126.6, 122.0, 110.2,
82.3, 60.7, 57.0, 34.8, 29.5, 29.1, 21.6, 20.9; IR (KBr): 3081, 2936, 1752, 1646, 1592, 1498,

(3) Klein, E.; Ohloff, G. Tetrahedron 1963, 19, 1091-1099.

(4) Narayanaswamy, M.; Sathe, V. M.; Rao, A. S. Chem. Ind. (London) 1969, 921-
922.

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II. Preparation of Thionocarbonate Derivatives

1458, 1380, 1273, 1202, 1032, 981, 771, 686; mp: 72-75 oC; HRMS (FAB, m/e) calcd for
C17 H 20 0 3 S (M+H) 305.1211; found 305.1210.
O-Octadecyl-O-phenylthionocarbonate (Table 1, entry 6). The general procedure

was followed using 1-octadecanol (3.00 g, 11.0 mmol; reaction time: 24 h).

Purification by recrystallization from EtOH afforded 3.50 g (78%) of the desired

product. 1H NMR (CDCl 3 ): 5 7.44 (t, J = 6.7, 2H), 7.30 (t, J = 7.5, 1H), 7.13 (d, J = 7.8, 2H),
13C
4.5 (t, J = 6.7, 2H), 1.87-1.43 (m, 2H), 1.50-1.22 (m, 30 H), 0.90 (t, J = 6.9, 3H); NMR

(CDCl 3 ): 8 195.5, 153.6, 129.7, 126.7, 122.2, 74.8, 32.1, 29.9, 29.8, 29.7, 29.6, 29.4, 28.4, 26.0,
22.9, 14.3; IR (KBr): 2918, 2849, 1587, 1487, 1474, 1463, 1389, 1287, 1192, 1068, 1015, 1002,
771, 690; mp: 52-54 'C; Anal. Calcd for C25H420 2 S: C, 73.84; H, 10.41. Found: C, 74.02;
H, 10.52.

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C1997 American Chemical Society J. Am. Chem. Soc. V 119 Page6949 Lopez Supplemental Page 7

III. Bu 3 SnH-Catalyzed Barton-McCombie Deoxygenation Reactions

The yields reported in Table 1 are the average of two runs.

General Procedure. PMHS (300 mg, 5.00 mmol), n-butanol (500 gL, 5.46 mmol),
AIBN (25 mg, 0.15 mmol), and (Bu 3 Sn)20 (19 gL, 0.037 mmol) were added to a
solution of thionocarbonate (1.00 mmol) in toluene (1 mL). The mixture was
allowed to stir at the specified temperature (vide infra). After 4-8 h, more AIBN (25
mg, 0.15 mmol) and (Bu 3 Sn) 2 0 (19 gL, 0.037 mmol) were added. After stirring for
the specified time, the reaction was cooled to room temperature, diluted with THF
(10 mL), and transferred to a 100 mL round-bottom flask. Aqueous sodium
hydroxide (2 N; 10 mL) was added SLOWLY to the rapidly stirring solution. The
mixture was stirred, loosely capped, for 3-8 h, and then the resulting cloudy solution
was extracted with Et 2 O (2 x 15 mL). The combined organic layers were washed (2 x
10 mL, 1 N HCl; 1 x 15 mL, brine), dried, filtered, and concentrated to afford the
crude product.
Cyclododecane (Table 1, entry 1). Following the general procedure, 0-
cyclododecyl-0-phenylthionocarbonate (320 mg, 1.00 mmol) was reduced at 80 oC in

6 h. The product was purified by flash chromatography (hexanes), which afforded

118 mg (70%) of cyclododecane. 1H NMR (CDCl 3 ): 8 1.35 (s, 24 H); 13C NMR (CDCl3 ):
8 24.0. The spectroscopic data are consistent with the literature data (The Aldrich
Library of NMR Spectra).
1,2-Diphenyl-1-methoxyethane (Table 1, entry 2). Following the general
procedure, 1,2-diphenyl-2-methoxy-1-0-(phenoxythiocarbonyl)ethane (364 mg, 1.00
mmol) was reduced at 80 oC in 24 h. Purification by flash chromatography
(hexanes/EtOAc, 99/1) afforded 165 mg (71%) of the desired product as a colorless oil.
1H NMR (CDCl 3 ): 8 7.35-7.12 (m, 10H), 4.36 (dd, J = 7.6, 5.8, 1H), 3.22 (s, 3H), 3.15 (dd, J
= 13.8, 7.6, 1H), 2.92 (dd, J = 13.7, 5.8, 1H); 13 C NMR (CDC13 ): 8 141.8, 138.7, 129.7, 128.5,

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C1997 American Chemical Society J. Am. Chem. Soc. V 119 Page6949 Lopez Supplemental Page 8

III. Bu 3 SnH-Catalyzed Barton-McCombie Deoxygenation Reactions

128.3, 127.8, 127.0, 126.3, 85.3, 57.0, 45.0; IR (neat): 2922, 2851, 1603, 1454, 1101, 1072,
1029, 699; HRMS (EI, m/e) calcd for C1 sH 16 0 (M+) 212.1201; found 212.1202.
1-Deoxy-2,3;5,6-di-O-isopropylidene-D-mannofuranose (Table 1, entry 3).

Following the general procedure, 2,3;5,6-di-O-isopropylidene-1-O-

phenoxythiocarbonyl-a-D-mannofuranoside (396 mg, 1.00 mmol) was reduced in

refluxing toluene in 24 h. Purification by flash chromatography (hexanes/EtOAc,

10/1) afforded 148 mg (61%) of the desired product as a colorless oil. 1H NMR
(CDCl 3 ): 8 4.81-4.72 (m, 2H), 4.41 (m, 1H), 4.12-4.01 (m, 3H), 3.53-3.46 (m, 2H), 1.49 (s,

3H), 1.45 (s, 3H), 1.38 (s, 3H), 1.34 (s, 3H); 13C NMR (CDCl 3 ): 8 112.3, 109.0, 82.8, 81.0,
80.4, 73.3, 73.1, 66.8, 26.9, 25.9, 25.3, 24.5; IR (neat): 2987, 2949, 2867, 1380, 1371, 1261,
1209, 1117, 1073, 847; HRMS (FAB, m/e) calcd for C12 H 2 0 0 5 (M+H) 245.1389; found
245.1388.
3-Deoxy-1,2;5,6-di-O-isopropylidene-ax-D-glucofuranoside (Table 1, entry 4).

Following the general procedure, 1,2;5,6-di-O-isopropylidene-3-O-

phenoxythiocarbonyl-a-D-glucofuranose (396 mg, 1.00 mmol) was reduced at 80 'C

in 8 h. Purification by flash chromatography (hexanes/EtOAc, 10/1) afforded 189 mg

(77%) of the desired product. 1H NMR (CDCl3): 8 5.81 (d, J = 3.7, 1H), 4.75 (m, 1H),
4.12 (m, 3H), 3.82 (m, 1H), 2.18 (dd, J = 3.4, 13.8, 1H), 1.76 (m, 1H), 1.51 (s, 3H), 1.42 (s,

3H), 1.35 (s, 3H), 1.31 (s, 3H); 13C NMR (CDC13 ): 8 111.5, 109.8, 105.8, 80.6, 78.8, 77.0,
67.3, 35.4, 26.9, 26.6, 26.3, 25.3. The spectroscopic data are consistent with the
literature data.5

(-)-Carveol (Table 1, entry 5). Following the general procedure, 5-isopropenyl-2-

methyl-2,3-oxy-1-O-phenoxythiocarbonylcyclohexane (304 mg, 1.00 mmol) was

reduced in refluxing toluene in 6 h. Purification by flash chromatography

(5) Robins, M. J.; Wilson, J. S.; Hansske, F. J. Am. Chem. Soc. 1983, 105, 4059-4065.

8
C1997 American Chemical Society J. Am. Chem. Soc. V 119 Page6949 Lopez Supplemental Page 9

III. Bu 3 SnH-Catalyzed Barton-McCombie Deoxygenation Reactions

(hexanes/EtOAc, 97/3) afforded 110 mg (72%) of the desired product. 1H NMR

(CDCl 3 ): 8 5.60 (m, 1H), 4.75 (m, 2H), 4.04 (br s, 1H), 2.41-2.27 (m, 1H), 2.19-2.21 (m,

1H), 1.99-1.80 (m, 2H), 1.81 (s, 3H), 1.76 (s, 3H), 1.67 (td, J = 4.0, 13.2, 1H), 1.55 (s, 1H);
13 C NMR (CDC13 ): 8 149.4, 134.5, 125.6, 109.2, 68.8, 36.9, 35.4, 31.2, 21.1, 21.0. The
spectroscopic data are consistent with the literature data (The Aldrich Library of

NMR Spectra).
Octadodecane (Table 1, entry 6). Following the general procedure, O-octadecyl-O-

phenylthionocarbonate (406 mg, 1.00 mmol) was reduced in refluxing toluene in 24

h; in this case, however, a total of 12 mol % of (Bu 3 Sn) 2 0 (61 gL, 0.12 mmol) and 40
mol % of AIBN (66 mg, 0.4 mmol) were used. Purification by flash chromatography

(hexanes) afforded 172 mg (68%) of the desired product. 1H NMR (CDC13 ): 8 1.46-1.22
(m, 32H), 0.91 (m, 6H); 13 C NMR (CDC13 ): 8 32.3, 30.1, 29.7, 23.1, 14.1. The

spectroscopic data are consistent with the literature data (The Aldrich Library of

NMR Spectra).

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C 1997 American Chemical Society J. Am. Chem. Soc. V 119 Page6949 Lopez Supplemental Page 10

IV. Stoichiometric Barton-McCombie Deoxygenation Reactions

General Procedure. Bu 3 SnH (2 equiv) and AIBN (0.3 equiv) were added to a 0.1
M solution of the thionocarbonate in toluene. The mixture was heated to the
specified temperature for the specified time (vide infra). The reaction was then
cooled to room temperature and worked up as described.
Cyclododecane (Table 1, entry 1). Following the general procedure, the

thionocarbonate (320 mg, 1.00 mmol) was deoxygenated at 80 oC in 2.5 h. The

reaction mixture was concentrated, and the residue was refluxed for 3 h in CCl4 (25
mL). After evaporation, 12 (in Et 2 0) was added until the iodine color persisted. The
solution was diluted with Et 2 0 (50 mL) and shaken with 10% KF solution (10 mL). 6
Filtration, extraction, drying, and evaporation gave the crude product, which was
purified by flash chromatography (pentane) to afford crystalline cyclododecane (115
mg, 68%).
1,2-Diphenyl-1-methoxyethane (Table 1, entry 2). Following the general
procedure, the thionocarbonate (100 mg, 0.270 mmol) was deoxygenated at 80 oC in 6
h. The desired product was purified by flash chromatography (hexanes/EtOAc,
99.75/0.25), which afforded 38 mg (65%) of the desired product.
1-Deoxy-2,3;5,6-di-O-isopropylidene-D-mannofuranose (Table 1, entry 3).
Following the general procedure, the thionocarbonate (100 mg, 0.250 mmol) was
deoxygenated in refluxing toluene in 6 h. Flash chromatography (hexanes/EtOAc,
90/10) afforded 45 mg (72%) of the desired product.
3-Deoxy-1,2;5,6-di-O-isopropylidene-c-D-glucofuranoside (Table 1, entry 4).
Following the general procedure, the thionocarbonate (100 mg, 0.250 mmol) was

(6) Barton, D. H. R.; Motherwell, W. B.; Stange, A. Synthesis 1981, 743-745.

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IV. Stoichiometric Barton-McCombie Deoxygenation Reactions

deoxygenated at 80 oC in 3 h. Flash chromatography (hexanes/EtOAc, 97/3) afforded

49 mg (79%) of the desired product.
(-)-Carveol (Table 1, entry 5). Following the general procedure, the
thionocarbonate (100 mg, 0.330 mmol) was deoxygenated in refluxing toluene in 1 h.
Flash chromatography (hexanes/EtOAc, 98/2) afforded 37 mg of the desired product,
contaminated with an unidentified impurity (repeated attempts to remove this
impurity were unsuccessful). Analysis by 1 H NMR using an internal standard
provided a corrected yield of 30 mg (61%).
Octadodecane (Table 1, entry 6). Following the general procedure, the
thionocarbonate (406 mg, 1.00 mmol) was deoxygenated in refluxing toluene in 19 h.
The desired product was purified as for cyclododecane (vide supra), affording 174 mg
(68%) of the desired product.

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C1997 American Chemical Society J. Am. Chem. Soc. V 119 Page6949 Lopez Supplemental Page 12

V. Equations 2 and 3

Preparation of Bu 3 SnOPh. (Bu 3 Sn) 2 0 (11.7 g, 9.80 mmol) and phenol (3.70 g, 19.6
mmol) were dissolved in toluene (30 mL) in a round-bottom flask equipped with a

reflux condenser and a Dean-Stark trap. The mixture was heated to reflux for 18 h.

The toluene was then removed at atmospheric pressure (under argon), and the

Bu 3 SnOPh was purified by vacuum distillation (140 oC, 0.4 mm; lit:7 152 'C, 1 mm),

which afforded 11.2 g (75%) of a colorless oil. 1H NMR (C6 D 6 ): 8 7.21-7.17 (m, 2H),

6.88-6.76 (m, 3H), 1.60-1.49 (m, 6H), 1.31-1.19 (m, 6H), 1.18-1.01 (m, 6H), 0.84 (t, J = 7.2,
119 Sn NMR
9H); 13C NMR (C6 D6 ): 6 163.7, 130.1, 120.3, 118.9, 28.5, 27.7, 16.4, 14.1;

(C6 D6 ): 8 107.6.
Reduction of (Bu 3 Sn)2 0 by PMHS dimer (eq 2). PMHS dimer (233 mg, 0.820
mmol), n-butanol (450 gL, 4.92 mmol), and heptadecane (46.0 [LL, 0.148 mmol;
internal standard) were added to a solution of (Bu 3 Sn) 2 0 (38.0 [LL, 0.074 mmol) in

toluene (1.0 mL). The resulting mixture was allowed to stir at 80 oC. Aliquots were

removed at different times and analyzed by GC (calibrated) to determine the extent

of formation of Bu 3 SnH. After 4.0 h, 2 equivalents of Bu 3 SnH had formed.

The same reaction was carried out in the absence of n-butanol. After 4.0 h, 1

equivalent of Bu 3 SnH had formed.

Reduction of Bu 3 SnOPh by PMHS dimer. PMHS dimer (233 mg, 0.820 mmol), n-

butanol (450 p.L, 4.92 mmol), and heptadecane (23.0 pL, 0.074 mmol; internal
standard) were added to a solution of Bu 3 SnOPh (28.0 p.L, 0.074 mmol) in toluene

(1.0 mL). The resulting mixture was allowed to stir at 80 oC. Aliquots were removed

(7) Poller, R. C. The Chemistry of Organotin Compounds; Logos: London, 1970; p

69.

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V. Equations 2 and 3

at different times and analyzed by GC (calibrated) to determine the extent of

formation of Bu 3 SnH. After 1.0 h, 43% conversion was observed.
The same reaction was carried out in the absence of n-butanol. After 1.0 h, <5%

conversion was observed.

13