SYNTHESIS AND OXIDATION OF SULFIDES
337
34.29 (C12), 35.17 (C8), 36.90 (C3), 37.37 (C5), 39.61
(C1), 45.62 (C16′), 48.44 (C16), 48.77 (C4), 53.22 (C9),
56.72 (C2), 126.73 (C20′), 128.80 (C20), 127.96 (C18′,
C22′), 128.06 (C18, C22), 128.92 (C19′, C22′), 129.01 (C19,
C21), 138.42 (C17′), 138.91 (C17). Mass spectrum, m/z
(Irel, %): 450 (7) [M]+, 339 (8), 344 (2), 327 (90), 298
(1), 271 (2), 235 (33), 203 (93), 177 (18), 161 (10),
147 (22), 107 (75), 95 (100), 69 (50), 41 (32), 4 (2).
C29H38S2. Calculated: M 450.
Oxidation of sulfides with m-chloroperoxyben-
zoic acid (m-CPBA) (general procedure). Sulfide 2,
3/4, or 6, 1 mmol, was dissolved in 8 mL of chloro-
form, a solution of 295 mg (1.2 mmol; in the synthesis
of sulfoxides) or 495 mg (2.0 mmol; in the synthesis of
sulfones) of 70% m-CPBA in 2 mL of chloroform was
added, and the mixture was stirred until the reaction
was complete. The mixture was then treated with
ammonium hydrogen carbonate and stirred for 15 min,
the precipitate was filtered off, the filtrate was evap-
orated, and the residue was subjected to silica gel
column chromatography.
0.69 d (1H, 3-H, J = 12.98 Hz), 0.78 s (3H, C14H3),
0.95 s (3H, C13H3), 1.05–1.11 m (1H, 7-H), 1.13 s (3H,
C15H3), 1.26–1.32 m (1H, 6-H), 1.33–1.37 m (1H,
7-H), 1.37–1.46 m (1H, 11-H), 1.45–1.49 m (1H, 5-H),
1.46–1.50 m (1H, 6-H), 1.55–1.60 m (1H, 3-H), 1.60–
1.64 m (1H, 12-H), 1.65–1.72 m (1H, 10-H), 1.87–
1.91 m (1H, 11-H), 1.96–2.04 m (1H, 10-H), 2.07–
2.19 m (1H, 12-H), 2.22 s (1H, OH), 2.57 d.d (1H,
2-H, J = 5.70, 7.13 Hz), 3.32 s (1H, 9-H), 3.87–4.25 m
(2H, 16-H), 7.34–7.45 m (5H, C6H5). 13C NMR spec-
trum, δC, ppm: 20.48 (C6), 24.87 (C14), 26.23 (C10),
28.21 (C13), 29.69 (C11), 30.35 (C15), 32.74 (C7), 34.80
(C12), 36.58 (C3), 39.14 (C1), 44.21 (C4), 51.45 (C5),
57.64 (C16), 66.47 (C2), 74.22 (C9), 128.26 (C17),
129.02 (C18, C22), 129.76 (C19, C21), 130.83 (C17).
Mass spectrum, m/z (Irel, %): 361 (1) [M + H]+, 344
(7), 235 (5), 203 (43), 161 (20), 49 (20), 147 (8), 119
(15), 95 (19), 93 (14), 91 (100), 65 (7), 55 (8), 44
(100), 41 (8), 18 (4), 4 (10). C29H38O2S. Calculated:
[M + H]+ 361.
(1S,2S,5S,8R,9R)-4,4,8-Trimethyl-2-(phenyl-
methanesulfonyl)tricyclo[6.3.1.01,5]dodecan-9-ol
(12). Yield 39%, Rf 0.31 (CHCl3–i-PrOH, 50:2.5),
[α]D24 = +13.73 (c = 0.17, CHCl3). IR spectrum, ν, cm–1:
(1S,2S,5S,8R,9R)-4,4,8-Trimethyl-2-(phenyl-
methanesulfinyl)tricyclo[6.3.1.01,5]dodecan-9-ol
(11a). Yield 46%, Rf 0.22 (CH2Cl2–i-PrOH, 50:4),
[α]D26 = +57.27 (c = 0.11, CHCl3). IR spectrum, ν, cm–1:
1
3531 (OH); 1290, 1117 (SO2). H NMR spectrum, δ,
ppm: 0.78 s (3H, C14H3), 0.95 s (3H, C13H3), 1.05–
1.11 m (1H, 7-H), 1.13 s (3H, C15H3), 1.24 d (1H, 6-H,
J = 6.23 Hz), 1.33–1.73 m (1H, 7-H), 1.37–1.45 m
(1H, 6-H), 1.46–1.54 m (1H, 11-H), 1.50–1.54 m (1H,
5-H), 1.60–1.65 m (1H, 10-H), 1.65–1.71 m (1H, 3-H),
1.69–1.77 m and 1.87–1.98 m (1H each, 12-H), 1.92–
2.03 m (1H, 11-H), 2.04–2.12 m (1H, 3-H), 2.17–
2.32 m (1H, 11-H), 5.27 d.d (1H, 2-H, J = 5.43,
7.98 Hz), 3.27 s (1H, 9-H), 4.11–4.30 m (2H, 16-H),
7.36–7.49 m (5H, C6H5). 13C NMR spectrum, δC, ppm:
20.44 (C6), 24.18 (C14), 25.75 (C10), 27.97 (C11), 28.19
(C13), 30.24 (C15), 32.46 (C7), 36.38 (C12), 39.46 (C1),
42.27 (C3), 45.96 (C4), 51.23 (C5), 61.27 (C16), 67.47
(C2), 74.42 (C9), 128.65 (C17), 128.94 (C18, C22),
130.40 (C19, C22), 131.35 (C20). Mass spectrum, m/z
(Irel, %): 376 (1) [M]+, 221 (3), 203 (30), 164 (12), 133
(8), 107 (35), 91 (100), 69 (31), 43 (25). C22H32O3S.
Calculated: M 376.
1
3388 (OH), 1026 (C–O). H NMR spectrum, δ, ppm:
0.78 s (3H, C14H3), 0.95 s (3H, C13H3), 1.05–1.11 m
(1H, 7-H), 1.13 s (3H, C15H3), 1.24 d (1H, 6-H, J =
6.23 Hz), 1.33–1.73 m (1H, 7-H), 1.37–1.45 m (1H,
6-H), 1.46–1.54 m (1H, 11-H),1.51–1.56 m (1H, 5-H),
1.60–1.65 m (1H, 10-H), 1.65–1.71 m (1H, 3-H),
1.69–1.77 m and 1.87–1.98 m (1H each, 12-H), 1.92–
2.03 m (1H, 10-H), 2.04–2.12 m (1H, 3-H), 2.17–
2.32 m (1H, 11-H), 2.85 d.d (1H, 2-H, J = 5.61,
8.25 Hz), 2.94 br.s (1H, OH), 3.27 s (1H, 9-H), 4.11–
4.30 m (2H, 16-H), 7.36–7.49 m (5H, C6H5). 13C NMR
spectrum, δC, ppm: 20.49 (C6), 24.55 (C14), 25.72
(C10), 28.24 (C13), 28.48 (C11), 30.39 (C15), 32.62 (C7),
34.90 (C8), 37.27 (C12), 40.58 (C3), 40.86 (C1), 45.89
(C4), 51.67 (C5), 56.53 (C16), 69.96 (C2), 74.65 (C9),
128.62 (C20), 128.80 (C18, C22), 129.96 (C17), 130.33
(C19, C20, C21). Mass spectrum, m/z (Irel, %): 361 (1)
[M + H]+, 293 (7), 269 (2), 221 (2), 203 (42), 161 (5),
147 (8), 133 (8), 91 (8), 55 (9), 41 (8). C22H32O2S.
Calculated: M + H 361.
(1S,2S,6S,9R)-2,6,10,10-Tetramethyl-2-(phenyl-
methanesulfonyl)bicyclo[7.2.0]undecan-5-one (13).
(1S,2S,5S,8R,9R)-4,4,8-Trimethyl-2-(phenyl-
methanesulfinyl)tricyclo[6.3.1.01,5]dodecan-9-ol
(11b). Yield 28%, Rf 0.17 (CH2Cl2–i-PrOH, 50:4),
[α]D26 = +80.00 (c = 0.10, CHCl3). IR spectrum, ν, cm–1:
Yield 84%, Rf 0.22 (CHCl3–Et2O, 10:1), [α]D24
=
+3.33° (c = 0.030, CHCl3). IR spectrum, ν, cm–1: 1708
1
(C=O); 1294, 1132 (SO2). H NMR spectrum, δ, ppm:
0.94 d (6H, C12H3, C13H3, J = 9.83 Hz), 1.07 d (3H,
C14H3, J = 6.79 Hz), 1.27–1.30 m (1H, 8-H), 1.31–
1
3406 (OH), 1024 (C–O). H NMR spectrum, δ, ppm:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 3 2016