The Journal of Organic Chemistry
ARTICLE
column chromatography on silica gel (CH2Cl2/EtOAc = 2:1) afforded
22b (102 mg, 0.40 mmol) in a 100% isolated yield (dr 100:0) as a white
solid. Mp: 91.5 °C. [R]D =ꢀ173.5° (c= 1.10, acetone). 1HNMR(500 MHz,
CDCl3), δ: 7.52 (d, 2H, J = 8.0 Hz), 7.28 (d, 2H, J = 8.0 Hz), 6.07
(s, 1H), 4.64 (dd, 1H, J = 3.7 Hz, 4.9 Hz), 2.60(m, 1H), 2.40 (s, 3H),
1.81ꢀ1.92 (m, 4H), 1.10 (d, 3H, J = 6.6 Hz), 0.97 (d, 3H, J = 6.9 Hz)
ppm. 13C{1H} NMR (125 MHz, CDCl3), δ: 151.9, 141.6, 141.1, 134.3,
130.0, 124.3, 32.1, 21.3, 19.1, 18.8, 18.3 ppm. IR (KBr): 3363, 2960, 2366,
1623, 1440, 1308, 1083, 999, 797 cmꢀ1. HRMS (FABþ) Calcd for
C14H21O2S [M þ H]þ: 253.12622; found: 253.12615. LRMS (FABþ):
253 (100), 235 (25), 191 (13), 123 (13).
13C{1H} NMR (125 MHz, CDCl3), δ: 152.8, 141.5, 140.8, 140.7, 132.7,
130.1, 128.4, 127.6, 126.1, 124.5, 71.6, 21.4, 18.1 ppm. IR (KBr): 3330,
3029, 2950, 2917, 1601, 1492, 1444, 1374, 1266, 1082, 1030, 833, 802,
730, 622 cmꢀ1. HRMS (FABþ) Calcd for C17H19O2S [M þ H]þ:
287.11057; found: 287.11048. LRMS (FABþ): 287 (100), 269 (70), 253
(13), 129 (69), 123 (32).
(E)-(3RS,Ss)-1-(Tributylstannyl)-3-(triethylsilyloxy)-1-(4-tolylsulfinyl)-
butene (24). Under argon atmosphere, a 25 mL two-necked round-
bottom flask equipped with a magnetic stir bar was charged sequentially
with (3RS,Ss)-1-(4-tolylsulfinyl)-3-(triethylsilyloxy)-1-butyne 18a (0.748 g,
2.32 mmol), toluene (15 mL), Pd(PPh3)4, (0.054 g, 0.046 mmol), and
Bu3SnH (ca. 0.71 mL, 2.32 mmol). The mixture was stirred at ꢀ20 °C
for 1 h. After removal of the solvent under reduced pressure, the residue
was diluted with light petroleum ether and filtered to remove the
palladium catalyst. The resulting solution wasconcentratedunder reduced
pressure, and the residue was subjected to flash column chromatography
on silica gel (eluent: hexane/EtOAc = 5:1) to give diastereomeric
mixture of (E)-(3RS,Ss)-1-(tributylstannyl)-3-(triethylsilyloxy)-1-(4-
tolylsulfinyl) butene 24 (1.07 g, 1.75 mmol, dr 1:1) in a 75% yield as a
yellow oil. 1H NMR (600 MHz, CDCl3), δ: 7.54 (d, 2H, J = 8.2 Hz), 7.39
(d, 2H, J = 8.3 Hz), 7.25ꢀ7.27 (m, 4H), 6.21 (d, 1H, J = 8.2 Hz), 6.17 (d,
1H, J= 6.5 Hz), 4.92ꢀ4.99 (m, 2H), 2.39(s, 3H), 2.39 (s, 3H), 1.18ꢀ1.44
(m, 36H), 0.98 (t, 9H, J = 8.25 Hz), 0.94 (t, 9H, J = 7.90 Hz), 0.80ꢀ0.92
(m, 24H), 0.66 (q, 6H, J = 7.90 Hz), 0.59 (q, 6H, J = 7.21 Hz) ppm.
13C{1H} NMR (150 MHz, CDCl3), δ: 153.8, 152.1, 151.7, 142.4, 142.3,
140.4, 140.2, 129.7, 129.5, 125.1, 124.9, 68.1, 66.7, 28.78, 28.77, 28.71,
27.29, 27.24, 24.6, 24.1, 21.3, 13.64, 13.63, 11.60, 11.56, 6.8, 5.0, 4.8 ppm.
IR (neat): 2954, 1460, 1415, 1375, 1240, 1136, 1082, 1039, 1012, 806,
744, 673 cmꢀ1. HRMS (FABþ) Calcd for C29H55O2SiSSn [M þ H]þ:
615.27139; found: 615.27096. LRMS (FABþ): 615 (8), 557 (100), 483
(10), 291 (7), 159 (41), 115 (100).
(Z)-(6RS,Ss)-6-(Triethylsilyloxy)-4-(4-tolylsulfinyl)hepta-1,4-diene (25a).
(E)-(3RS,Ss)-1-(Tributylstannyl)-3-(triethylsilyloxy)-1-(4-tolylsulfinyl)-
1-butene 24 (0.300 g, 0.489 mmol) and 3-bromo-1-propene (48.0 μL,
0.565 mmol) were dissolved in 5.2 mL of DMF at room temperature
under argon atmosphere. To this solution were then added Pd(PPh3)4
(0.030 g, 0.026 mmol) and CuI (0.073 g, 0.386 mmol). The mixture was
stirred at room temperature, and the reaction progress was monitored
by TLC for the disappearance of the starting organostannane. Upon
completion of the reaction, the mixture was diluted with EtOAc and
washed with brine. The organic layer was separated and dried over
anhydrous Na2SO4. The solvent was removed under reduced pressure,
and the residue was subjected to flash column chromatography on silica
gel (eluent: hexane/EtOAc = 5:1) to give diastereomeric mixture of
(Z)-(6RS,Rs)-6-(triethylsilyloxy)-4-(4-tolylsulfinyl)hept-1,4-diene 25a
(0.165 g, 0.453 mmol, dr 1:1) in a 93% yield as a colorless oil.
(Z)-(Rs,3R)-3-Phenyl-1-(4-tolylsulfinyl)-1-propen-3-ol (22c). Proce-
dure A. 21c (55 mg, 0.192 mmol), LaCl3 7H2O (143 mg, 0.384 mmol),
3
NaBH4 (14.5 mg, 0.384 mmol), MeOH (2.0 mL). Purification by means
of column chromatography on silica gel (eluent: CH2Cl2/EtOAc = 3:1)
afforded 22c (55 mg, 0.192 mmol) in a 100% isolated yield (dr 100:0) as
1
a white solid. Mp: 160.5 °C. [R]D = ꢀ0.102° (c = 1.02, acetone). H
NMR (500 MHz, CDCl3), δ: 7.57 (d, 2H, J = 8.0 Hz), 7.48 (d, 2H, J =
7.7 Hz), 7.35 (t, 3H, J = 7.1 Hz), 7.28 (d, 2H, J = 8.3 Hz), 6.24 (d, 1H, J =
4.0 Hz), 6.10 (d, 1H, J = 1.1 Hz), 3.43 (d, 1H, J = 4.0 Hz), 2.40 (s, 3H),
1.69 (d, 3H, J = 1.43 Hz) ppm. 13C{1H} NMR (125 MHz, CDCl3), δ:
151.3, 141.5, 141.3, 140.4, 134.0, 130.1, 128.6, 127.9, 125.8, 124.4, 72.5,
21.4, 18.3 ppm. IR (KBr): 3314, 2920, 2361, 1598, 1492, 1446, 1290,
1086, 1057, 1005, 846, 819, 744, 636, 481 cmꢀ1. HRMS (FABþ) Calcd
for C17H19O2S [M þ H]þ: 287.11057; found: 287.11053. LRMS
(FABþ): 287 (100), 269 (46), 253 (18), 129 (45).
(Z)-(Rs,3R)-2-Methyl-1-(4-tolylsulfinyl)-1-buten-3-ol (23a). Proce-
dure B. 21a (75 mg, 0.328 mmol), LaCl3 (161 mg, 0.656 mmol), DIBAL
(1.01 M solution in toluene, 0.65 mL, 0.66 mmol), THF (3.3 mL).
Purification by means of column chromatography on silica gel (eluent:
CH2Cl2/EtOAc = 1:3) afforded 23a (65 mg, 0.290 mmol) in an 89%
isolated yield (dr 0:100) as a white emulsion . [R]D = ꢀ241.7° (c = 1.05,
acetone). 1H NMR (600 MHz, CDCl3), δ: 7.48 (d, 2H, J = 7.9 Hz), 7.31
(d, 2H, J = 8.5 Hz), 5.96 (s, 1H), 5.28ꢀ5.32 (m, 1H), 3.54 (m, 1H), 2.41
(s, 3H), 1.90 (d, 3H, J = 1.4 Hz), 1.34 (d, 3H, 6.53 Hz) ppm. 13C{1H}
NMR (150 MHz, CDCl3), δ:154.2, 141.3, 141.0, 131.6, 130.1, 124.2,
66.2, 21.4, 17.6 ppm. IR (KBr): 3377, 2976, 2922, 1618, 1493, 1441,
1294, 1157, 1078, 1026, 908, 808, 740, 625 cmꢀ1. HRMS (FABþ) Calcd
for C12H17O2S [M þ H]þ: 225.09492; found: 225.09485. LRMS
(FABþ): 225 (35), 207 (10), 165 (5).
(Z)-(Rs,3R)-2,4-Dimethyl-1-(4-tolylsulfinyl)-1-penten-3-ol (23b). Pro-
cedure B. 21b (100 mg, 0.40 mmol), LaCl3 (196 mg, 0.799 mmol),
DIBAL (1.01 M solution in toluene, 0.80 mL, 0.80 mmol), THF (4 mL).
Purification by means of column chromatography on silica gel (eluent:
CH2Cl2/EtOAc = 2:1) afforded 23b (96 mg, 0.381 mmol) in a 95%
isolated yield (dr 2:98) as a white solid. Mp: 187 °C. [R]D = ꢀ251.0° (c =
1.07, acetone). 1H NMR (500 MHz, CDCl3), δ: 7.53 (d, 2H, J = 8.0 Hz),
7.31 (d, 2H, J = 8.1 Hz), 6.11 (d, 1H, J = 1.4 Hz), 4.69 (dd, 1H, J = 4.0 Hz,
5.1 Hz), 3.40 (d, 1H, J = 4.0 Hz), 2.40 (s, 3H), 1.84ꢀ1.90 (m, 4H), 1.13
(d, 3H, J= 6.3 Hz), 0.79 (d, 3H, J= 6.9 Hz) ppm. 13C{1H} NMR (125 MHz,
CDCl3), δ: 152.8, 141.3, 141.1, 133.8, 130.1, 124.5, 75.8, 31.7, 21.4, 19.4,
19.1, 18.0 ppm. IR (KBr): 3389, 2954, 2919, 2871, 2366, 1620, 1442,
1375, 1323, 1085, 1035, 813, 782, 626 cmꢀ1. HRMS (FABþ) Calcd for
C14H21O2S [M þ H]þ: 253.12622; found: 253.12623. LRMS (FABþ):
253 (100), 235 (33), 191 (12), 123 (13).
(Z)-(6S,Ss)-6-(Triethylsilyloxy)-4-(4-tolylsulfinyl)hepta-1,4-diene:
1
25a-(S) [R]D = ꢀ181.8° (c = 0.80, acetone). H NMR (600 MHz,
CDCl3), δ: 7.40 (d, 2H, J = 8.3 Hz), 7.29 (d, 2H, J = 7.9 Hz), 5.94ꢀ5.96
(m, 1H), 5.53ꢀ5.60 (m, 1H), 5.27ꢀ5.31 (m, 1H), 5.05 (d, 1H, J = 9.9 Hz),
4.96ꢀ5.00 (m, 1H), 3.13ꢀ3.17 (m, 1H), 2.52 (dd, 1H, J = 7.4 Hz, 9.6 Hz),
2.41 (s, 3H), 1.33 (d, 3H, J = 6.18 Hz), 0.99 (t, 9H, J = 8.25 Hz), 0.66
(q, 6H, J = 7.91 Hz) ppm. 13C{1H} NMR (150 MHz, CDCl3), δ: 142.1,
141.7, 140.9, 139.1, 134.1, 129.9, 124.3, 118.3, 64.1, 28.5, 24.8, 21.4, 6.8, 4.8
ppm. IR (neat): 2956, 2877, 1639, 1490, 1458, 1371, 1238, 1084, 1051,
1001, 918, 808, 775, 744 cmꢀ1. HRMS(FABþ) CalcdforC20H33O2SiS [M
þ H]þ: 365.19705; found: 365.19705. LRMS (FABþ): 365 (32), 347
(41), 335 (38), 233 (100), 123 (29), 115 (37).
(Z)-(Rs,3S)-3-Phenyl-1-(4-tolylsulfinyl)-1-propen-3-ol (23c). Proce-
dure B. 21c (100 mg, 0.352 mmol), LaCl3 (172 mg, 0.702 mmol),
DIBAL (1.01M solution intoluene, 0.70 mL, 0.70 mmol), THF (3.5 mL).
Purification by means of column chromatography on silica gel (eluent:
CH2Cl2/EtOAc = 2:1) afforded 23c (91 mg, 0.319 mmol) in a 91%
isolated yield (dr 14:86) as a white solid. Mp: 123.5 °C. [R]D = ꢀ93.6°
(c = 1.03, acetone). 1H NMR (500 MHz, CDCl3), δ: 7.51 (d, 2H, J = 8.3
Hz), 7.27ꢀ7.39 (m, 7H), 6.30(d, 1H, J= 3.7Hz), 6.16 (d, 1H, J= 1.1Hz),
4.57 (d, 1H, J = 4.0 Hz), 2.41 (s, 3H), 1.81 (d, 3H, J = 1.14 Hz) ppm.
(Z)-(6R,Ss)-6-(Triethylsilyloxy)-4-(4-tolylsulfinyl)hept-1,4-diene:
1
25a-(R) [R]D = ꢀ183.4° (c = 0.73, acetone). H NMR (600 MHz,
CDCl3), δ: 7.48 (d, 2H, J = 8.2 Hz), 7.30 (d, 2H, J = 8.0 Hz), 5.96ꢀ5.97
(m, 1H), 5.51ꢀ5.58 (m, 1H), 5.27ꢀ5.30 (m, 1H), 5.02ꢀ5.04 (m, 1H),
4.94ꢀ4.97 (m, 1H), 3.03 (dd, 1H, J = 6.5 Hz, 10.3 Hz), 2.46 (dd, 1H, J =
7.1 Hz, 9.7 Hz), 2.41 (s, 3H), 1.41 (d, 3H, J = 6.53 Hz), 0.98 (t, 9H, J =
3933
dx.doi.org/10.1021/jo200373a |J. Org. Chem. 2011, 76, 3922–3936