The Journal of Organic Chemistry
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purified by flash column chromatography (pentanes to 30:1 pentane/
Et2O eluent) to afford the thiol-ene adducts. Reactions without base-
sensitive substrates were first extracted twice with 10% NaOH (aq) to
remove unreacted thiol. The aqueous layers were extracted with Et2O,
and the combined organic layers were dried over Na2SO4, filtered, and
concentrated prior to column chromatography.
Benzyl(phenethyl)sulfane. (Table 2, entry 1) Colorless oil.
Experiment 1: 210 mg (0.980 mmol, 98% yield). Experiment 2: 208
mg (0.969 mmol, 97% yield). All spectroscopic data were consistent
with reported values.20
(s, 2H), 3.66−3.58 (m, 2H), 2.42 (dd, J = 12.7, 6.1 Hz, 1H), 2.32 (dd,
J = 12.7, 7.0 Hz, 1H), 1.84−1.74 (m, 1H), 1.71−1.63 (m, 1H), 1.48 (s,
1H), 1.45−1.36 (m, 1H), 0.98 (d, J = 6.7 Hz, 3H); 13C NMR (126
MHz, CDCl3) δ 138.5, 128.8, 128.4, 126.9, 60.7, 38.9, 38.8, 36.7, 29.7,
19.6; HRMS (EI) calcd for [C12H18OS]+ requires m/z 210.1073,
found m/z 210.1078.
Benzyl(1-phenylpropan-2-yl)sulfane. (Table 3, entry 4) Color-
less oil. Experiment 1: 213 mg (0.879 mmol, 88% yield). Experiment
2: 223 mg (0.920 mmol, 92% yield). IR (thin film) 3023, 1497, 1450
1
cm−1; H NMR (500 MHz, CDCl3) δ 7.40−7.06 (m, 10H), 3.71 (s,
2H), 2.98 (dd, J = 13.4, 5.7 Hz, 1H), 2.91−2.81 (m, 1H), 2.63 (dd, J =
13.4, 8.6 Hz, 1H), 1.18 (d, J = 6.7 Hz, 2H); 13C NMR (126 MHz,
CDCl3) δ 139.1, 138.5, 129.2, 128.8, 128.4, 128.2, 126.9, 126.2, 43.5,
40.6, 35.3, 20.4; HRMS (EI) calcd for [C16H18S]+ requires m/z
242.1124, found m/z 242.1117.
Methyl 2-(Phenethylthio)acetate. (Table 2, entry 2) Colorless
oil. Experiment 1: 200 mg (0.949 mmol, 95% yield). Experiment 2:
205 mg (0.975 mmol, 98% yield). IR (thin film) 1734,1647, 1283
1
cm−1; H NMR (500 MHz, CDCl3) δ 7.50−6.96 (m, 5H), 3.74 (s,
3H), 3.23 (s, 2H), 2.90 (apparent s, 4H); 13C NMR (126 MHz,
CDCl3) δ 170.8, 140.0, 128.5, 126.4, 52.4, 35.6, 34.0, 33.4; HRMS
(EI) calcd for [C11H14O2S + NH4]+ requires m/z 228.1053, found m/z
228.1053.
Benzyl(cyclohexyl)sulfane. (Table 3, entry 5) Colorless oil.
Experiment 1: 206 mg (0.998 mmol, 99% yield). Experiment 2: 201
mg (0.974 mmol, 97% yield). IR (thin film) 2932, 2856, 1497, 1450
1
cm−1; H NMR (500 MHz, CDCl3) δ 7.43−7.08 (m, 5H), 3.74 (s,
Cyclohexyl(phenethyl)sulfane. (Table 2, entry 3) Colorless oil.
Experiment 1: 214 mg (0.969 mmol, 97% yield). Experiment 2: 220
mg (0.998 mmol, 99% yield). IR (thin film) 2929, 2851, 1653, 1450
2H), 2.56 (ddd, J = 10.5, 6.8, 3.7 Hz, 1H), 2.01−1.85 (m, 2H), 1.74
(td, J = 6.0, 5.5, 2.9 Hz, 2H), 1.64−1.50 (m, 1H), 1.42−1.14 (m, 5H);
13C NMR (126 MHz, CDCl3) δ 141.6, 131.4, 131.1, 129.4, 45.6, 37.3,
36.1, 28.7, 28.5; HRMS (EI) calcd for [C13H18S]+ requires m/z
206.1124, found m/z 206.1132.
1
cm−1; H NMR (500 MHz, CDCl3) δ 7.59−6.96 (m, 5H), 2.87, 2.78
(AA′BB′, 4H), 2.65 (m, 1H), 2.01−1.94 (m, 2H), 1.85−1.70 (m, 2H),
1.64−1.57 (m, 1H), 1.40−1.17 (m, 4H); 13C NMR (126 MHz,
CDCl3) δ 140.8, 128.4, 126.2, 43.6, 36.7, 33.7, 31.6, 26.1, 25.8; HRMS
(EI) calcd for [C14H20S]+ requires m/z 220.1281, found m/z
220.1278.
Benzyl(2-methylcyclohexyl)sulfane. (Table 3, entry 6) Color-
less oil. Experiment 1: 155 mg (0.703 mmol, 70% yield, 5:1 dr,
trans:cis). Experiment 2: 167 mg (0.759 mmol, 76% yield, 5:1 dr,
trans:cis). IR (thin film) 3424, 2925, 2852, 1602, 1494, 1453 cm−1; 1H
NMR (500 MHz, C6D6) δ 7.44−6.71 (m, 5H), 3.48 (d, J = 4.7 Hz,
2H), 3.26 (dd, J = 7.3, 1.2 Hz, 1H), 2.81−2.46 (m, 1H), 2.15−1.83
(m, 1H), 1.76−1.08 (m, 9H), 1.07 (d, J = 6.5 Hz, 3H), 1.00 (d, J = 6.9
Hz, 3H); 13C NMR (126 MHz, CDCl3) δ 138.9, 129.4, 128.8, 128.5,
128.3, 128.0, 127.4, 126.7, 50.8, 48.9, 43.2, 37.4, 36.0, 35.6, 34.8, 34.7,
34.3, 31.3, 30.6, 26.7, 25.8, 23.6, 23.2, 21.0, 17.4; HRMS (EI) calcd for
[C14H19S]+ requires m/z 219.1202, found m/z 219.1203.
(E)-Benzyl(styryl)sulfane. (Table 3, entry 7) Colorless semisolid.
Experiment 1: 206 mg (0.911 mmol, 91% yield, 10:1 E:Z). Experiment
2: 200 mg (0.882 mmol, 88% yield, 9:1 E:Z). All spectroscopic data
were consistent with reported values.24
2-(Benzylthio)ethyl Acetate. (Table 3, entry 8) Colorless oil.
Experiment 1: 170 mg (0.810 mmol, 81% yield). Experiment 2: 175
mg (0.830 mmol, 83% yield). All spectroscopic data were consistent
with reported values.25
tert-Butyl(phenethyl)sulfane. (Table 2, entry 4) Colorless oil.
Experiment 1: 165 mg (0.848 mmol, 85% yield). Experiment 2: 167
mg (0.858 mmol, 86% yield). IR (thin film) 2967, 2865, 1504, 1467
1
cm−1; H NMR (500 MHz, CDCl3) δ 7.50−6.87 (m, 5H), 2.86, 2.78
(AA′BB′, 4H), 1.33 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 140.9,
128.4, 128.4, 126.2, 42.1, 36.4, 30.9, 29.9; HRMS (EI) calcd for
[C12H18S]+ requires m/z 194.1124, found m/z 194.1125.
(S)-Methyl 2-((tert-Butoxycarbonyl)amino)-3-(phenethyl-
thio)propanoate. (Table 2, entry 5). Colorless semisolid. Experi-
ment 1: 332 mg (0.977 mmol, 98% yield). Experiment 2: 327 mg
(0.962 mmol, 96% yield). IR (thin film) 3432, 2979, 2253, 1708, 1498
cm−1; 1H NMR (500 MHz, CDCl3) δ 7.35−7.12 (m, 5H), 5.41−5.30
(m, 1H), 4.54 (s, 1H), 3.75 (s, 3H), 2.97 (t, J = 5.0 Hz, 2H), 2.78, 2.86
(AA′BB′, 4H), 1.44 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 171.5,
140.0, 128.4, 128.4, 126.4, 94.7, 80.1, 53.3, 52.5, 36.1, 34.6, 34.1, 28.3;
HRMS (EI) calcd for [C17H25NO4S + Na]+ requires m/z 362.1397,
found m/z 362.1397.
3-(Benzylthio)propan-1-ol. (Table 3 entry 9) Colorless oil.
(S)-Phenethyl Ethanethioate. (Table 2, entry 6) Colorless oil.
Experiment 1: 167 mg (0.923 mmol, 92% yield). Experiment 2: 158
mg (0.877 mmol, 88% yield). All spectroscopic data were consistent
with reported values.21
Phenethyl(phenyl)sulfane. (Table 2, entry 7) Colorless oil.
Experiment 1: 210 mg (0.9803 mmol, 98% yield). Experiment 2: 208
mg (0.969 mmol, 97% yield). All spectroscopic data were consistent
with reported values.22
Benzyl(octyl)sulfane. (Table 3, entry 1) Colorless oil. Experiment
1: 234 mg (0.989 mmol, 99% yield). Experiment 2: 235 mg (0.992
mmol, 99% yield). All spectroscopic data were consistent with
reported values.23
Experiment 1:155 mg (0.846 mmol, 85% yield). Experiment 2:158 mg
1
(0.869 mmol, 87% yield). IR (thin film) 3426, 2908, 1647 cm−1; H
NMR (500 MHz, CDCl3) δ 7.39−7.17 (m, 5H), 3.73 (s, 2H), 3.73−
3.68 (m, 2H), 2.54 (t, J = 7.0 Hz, 2H), 1.85−1.75 (m, 2H), 1.53 (bs,
1H); 13C NMR (126 MHz, CDCl3) δ 138.3, 128.8, 128.5, 127.0, 61.8,
36.3, 31.5, 28.0; HRMS (EI) calcd for [C10H14OS + H]+ requires m/z
183.0839, found m/z 183.0833.
tert-Butyl (3-(Benzylthio)propyl)carbamate. (Table 3, entry
10) White solid. Experiment 1: 248 mg (0.881 mmol, 88% yield).
Experiment 2: 158 mg (0.869 mmol, 87% yield). IR (thin film) 3363,
1
2927, 2932, 2251, 1700, 1508 cm−1; H NMR (500 MHz, CDCl3) δ
7.76−6.80 (m, 5H), 4.58 (s, 1H), 3.69 (s, 2H), 3.16 (q, J = 7.4, 7.0 Hz,
2H), 2.43 (t, J = 7.2 Hz, 2H), 1.96−1.53 (m, 2H), 1.43 (s, 9H); 13C
NMR (126 MHz, CDCl3) δ 155.8, 138.3, 128.8, 128.4, 126.9, 79.1,
39.5, 36.2, 29.3, 28.4, 28.3.; HRMS (EI) calcd for [C15H23O2NS + H]+
requires m/z 282.1523, found m/z 282.1527.
Benzyl(cyclohexylmethyl)sulfane. (Table 3, entry 2) Colorless
oil. Experiment 1: 215 mg (0.974 mmol, 97% yield). Experiment 2:
219 mg (0.992 mmol, 99% yield). IR (thin film) 2925, 2852, 1497,
1
1450 cm−1; H NMR (500 MHz, CDCl3) δ 7.72−7.07 (m, 5H), 3.68
(s, 2H), 2.30 (d, J = 6.8 Hz, 2H), 1.84−1.75 (m, 3H), 1.73−1.58 (m,
3H), 1.42 (dddddd, J = 3.4, 3.4, 3.4, 3.4, 3.4, 3.4, 3.4 Hz, 1H), 1.27−
1.04 (m, 3H), 0.90 (ddd, J = 12.4, 2.1, 3.3 Hz, 2H); 13C NMR (126
MHz, CDCl3) δ 138.7, 128.8, 128.4, 126.8, 38.9, 37.6, 36.8, 32.8, 26.4,
26.1; HRMS (EI) calcd for [C14H20S]+ requires m/z 220.1281, found
m/z 220.1286.
Benzyl(3-chloropropyl)sulfane. (Table 3, entry 11) Colorless
oil. Experiment 1: 160 mg (0.801 mmol, 80% yield). Experiment 2:
159 mg (0.790 mmol, 79% yield). IR (thin film) 3030, 2921, 2258,
1497, 1450 cm−1; 1H NMR (500 MHz, CDCl3) δ 7.43−7.17 (m, 5H),
3.71 (s, 2H), 3.61 (t, J = 6.4 Hz, 2H), 2.57 (t, J = 7.0 Hz, 2H), 1.98 (tt,
J = 6.7, 6.7 Hz, 2H); 13C NMR (126 MHz, CDCl3) δ 140.9, 131.5,
131.2, 129.7, 46.1, 39.0, 34.5, 31.0; HRMS (EI) calcd for [C10H13ClS]+
requires m/z 200.0421, found m/z 200.0411.
4-(Benzylthio)-3-methylbutan-1-ol. (Table 3, entry 3) Colorless
oil. Experiment 1: 195 mg (0.930 mmol, 93% yield). Experiment 2:
202 mg (0.970 mmol, 97% yield). IR (thin film) 3384, 2927, 1494,
Benzyl(4-bromophenethyl)sulfane. (Table 3, entry 12) Color-
less oil. Experiment 1: 273 mg (0.890 mmol, 89% yield). Experiment
1
1454 cm−1; H NMR (500 MHz, CDCl3) δ 7.37−7.19 (m, 5H), 3.69
2049
dx.doi.org/10.1021/jo3020825 | J. Org. Chem. 2013, 78, 2046−2050