The Journal of Organic Chemistry
Article
1
1H NMR (600 MHz, CDCl3) δ 2.07 (ddd, J = 8, 10, 13 Hz, 1 H),
72.4% D (134 mg). H NMR (600 MHz, CDCl3) δ 1.56−1.65 (m, 1
H), 2.24−2.33 (m, 1 H), 2.86−2.96 (m, 1.47 H), 3.17 (dd, J = 6.3,
14.3 Hz, 1 H), 3.32−3.37 (m, 0.83 H), 3.52−3.61 (m, 1 H), 7.12−7.14
(m, 2 H), 7.15−7.20 (m, 1 H), 7.23−7.26 (m, 2 H). 13C NMR (125
MHz, CDCl3) δ 16.3, 16.4, 38.1, 48.1 (t, J = 22.4 Hz), 48.2 (t, J = 23.3
Hz), 48.5, 68.9, 127.0, 128.8, 128.9, 137.1. 153 ESI-MS: m/z (rel. int.):
203[MH + Na]+(34); 204 [MD + Na]+(100).
(1RS*,2R*,4R*)-2-Benzyl-4-(3-propenyl)thietane 1-Oxide
(1RS*,2R*,4R*)-6e. Column chromatography on silica gel (Hexane/
AcOEt 50:50), colorless oil. 35% (76 mg). 1H NMR (600 MHz,
CDCl3) δ 1.92 (ddd, J = 8, 11, 13 Hz, 1 H), 2.21 (ddd, J = 3, 10, 13
Hz, 1 H), 2.35−2.44 (m, 1 H), 2.69−2.77 (m, 1), 2.92 (dd, J = 9, 14
Hz, 1 H), 3.17 (dd, J = 6, 14 Hz, 1 H), 3.35−3.39 (m, 1 H), 3.58−3.64
(m, 1 H), 5.03−5.08 (m, 2 H), 5.68−5.77 (m, 1 H), 7.11−7.13 (m, 2
H), 7.16−7.19 (m, 1 H), 7.23−7.26 (m, 2 H). 13C NMR (125 MHz,
CDCl3) δ 23.4, 30.3, 38.1, 53.0, 65.2, 118.0, 127.0, 128.8, 128.9, 133.8,
137.3. FT-IR (film, cm−1) υ 701, 749, 917, 1005, 1062, 1437, 1454,
1496, 1602, 1639, 2929, 3028, 3062, 3445. HRMS (ESI-TOF) m/z [M
+ Na]+ calcd for C13H16SONa 243.0814; found 243.0818.
2.94−3.00 (m, 2 H), 3.15 (dd, J = 7, 14 Hz, 1 H), 3.80−3.86 (m, 1 H),
4.29 (ddd, J = 1, 6, 10 Hz, 1 H), 5.44 (bs, 1 H, OH), 7.08−7.11 (m, 3
H), 7.15−7.27 (m, 10H), 7.42−7.44 (m, 2 H). 13C NMR (125 MHz,
CDCl3) δ 23.9, 38.1, 55.4, 65.5, 80.2, 125.7, 125.9, 127.0, 127.2, 127.6,
128.4, 128.7, 128.89, 128.94, 136.9, 143.6, 145.9. FT-IR (KBr, cm−1) υ
675, 700, 759,769, 1016, 1033, 1060, 1178, 1193, 1407, 1450, 1493,
1601, 2919, 2935, 3025, 3308. HRMS (ESI-TOF) m/z [M + Na]+
calcd for C23H22SO2Na 385.1233; found 385.1216.
(1RS *,2R*,4S*)-2-Benzyl-4-methylthietane 1-Oxide
(1RS*,2R*,4S*)-6a. Column chromatography on silica gel (AcOEt),
pale yellow oil. 39% (75 mg). 1H NMR (500 MHz, CDCl3) δ 1.36 (q,
J = 12.2 Hz, 1H), 1.45 (d, J = 6.8 Hz, 3H), 2.49 (dt, J = 12.6, 9.5 Hz,
1H), 2.97 (dd, J = 14.2, 8.5 Hz, 1H), 3.18−3.23 (M, 1H), 3.25 (dd, J =
14.0, 6.4 Hz, 1H), 7.19 (d, J = 7.3 Hz, 2H), 7.24 (t, J = 7.4 Hz, 1H),
7.31 (t, J = 7.4 Hz, 2H).). 13C NMR (125 MHz, CDCl3) δ 16.8, 24.2,
37.9, 59.3, 64.2, 126.9, 128.64, 128.8, 137.2. FT-IR (film, cm−1) υ 702,
1065, 1376, 1453, 1496, 2925, 3467. HRMS (ESI-TOF) m/z [M +
Na]+ calcd for C11H14SONa 217.0658; found 217.0664.
(1RS*,2R*,4S*)-2-Benzyl-4-(3-propenyl)thietane 1-Oxide
(1RS *,2R*,4R*)-2-Benzyl-4-methylthietane 1-Oxide
(1RS*,2R*,4R*)-6a. Column chromatography on silica gel (AcOEt),
pale yellow oil, 31% (61 mg). 1H NMR (600 MHz, CDCl3) δ 1.49 (d,
J = 7 Hz, 3 H), 1.99−2.16 (m, 2 H), 2.98 (dd, J = 8, 14 Hz, 1 H), 3.24
(dd, J = 7, 14 Hz, 1 H), 3.52 (quintet, J = 7 Hz, 1 H), 3.69 (quintet, J =
8 Hz, 1 H), 7.10−7.37 (m, 5 H). 13C NMR (125 MHz, CDCl3) δ 11.6,
25.3, 38.0, 49.5, 65.3, 127.0, 128.8, 128.9, 137.4. FT-IR (film, cm−1) υ
702, 1065, 1376, 1453, 1496, 2925, 3467. HRMS (ESI-TOF) m/z [M
+ Na]+ calcd for C11H14SONa 217.0658; found 217.0661.
(1RS*,2S*,4S*)-2-[(4-Chlorophenyl)hydroxymethyl)]-4-benzyl-
thietane 1-Oxide (1RS*,2S*,4S*) 6b. Mixture of diastereomers at the
carbinolic carbon, dr 50:50. Column chromatography on silica gel
(AcOEt), colorless oil. 71% (224 mg). 1H NMR (600 MHz, CDCl3) δ
1.44 (q, J = 12.2 Hz, 1 H), 1.72 (q, J = 12.2 Hz, 1 H), 2.07−2.13 (m,
overlapping s Acetone at 2.09, 2 H), 2.83−2.90 (m, 2 H), 3.14−3.20
(m, 2 H), 3.26−3.37 (m, 4 H), 4.69 (d, J = 8.7 Hz, 1 H), 5.09 (d, J =
3.7 Hz, 1 H), 7.08−7.09 (m, 3 H), 7.15−7.25 (m, 15 H). 13C NMR
(125 MHz, CDCl3) δ 17.4, 20.4, 37.8, 63.3, 69.1, 70.1, 73.5, 127.1−
126.5, 128.6−129.1, 133.9, 133.3, 136.9, 137.0, 139.1, 139.2. FT-IR
(film, cm−1) υ 703, 735, 841, 1047, 1245, 1454, 1493, 1602, 1732,
2925, 3334. HRMS (ESI-TOF) m/z [M + Na]+ calcd for
C17H17ClSO2Na 343.0530; found 343.0516.
(1RS*,2R*,4S*)-4-Benzyl-2-(1-hydroxycyclohex-2-en-1-yl)thietane
1-Oxide (1RS*,2R*,4S*) 6c. Major diastereomer. Column chromatog-
raphy on silica gel (Hexane/AcOEt 50:50), pale yellow oil. 42% (110
mg). 1H NMR (600 MHz, CDCl3) δ 1.50−1.57 (m, 1 H), 1.75−1.82
(m, 1 H), 1.84−1.94 (m, 2 H), 1.98−2.44 (m, overlapping s, AcOEt, 2
H), 2.92−3.04 (m, 2 H), 3.14 (dd, J = 7, 14 Hz, 1 H), 3.30 (ddd, J = 6,
7, 15 Hz, 1 H), 3.87−3.97 (m, 1 H), 4.21 (bs, 1 H, OH), 5.54 (d, J =
10 Hz, 1 H), 5.80 (dt, J = 4, 1 Hz, 1 H), 7.13−7.14 (m, 2 H), 7.17−
7.20 (m, 1 H), 7.24−7.26 (m, 2 H). 13C NMR (125 MHz, CDCl3) δ
18.8, 22.7, 25.0, 35.8, 38.3, 57.2, 65.2, 72.9, 127.09, 127.14, 128.8,
128.9, 131.6, 137.0. FT-IR (film, cm−1) υ 700, 735, 1010, 1186, 1262,
1429, 1454, 1496, 1672, 1707, 2866, 2935, 3027, 3392. HRMS (ESI-
TOF) m/z [M + Na]+ calcd for C16H20SO2Na 299.1076; found
299.1078.
(1RS*,2R*,4S*)-4-Benzyl-2-(1-hydroxycyclohex-2-en-1-yl)thietane
1-Oxide (1RS*,2R*,4S*) 6c. Minor diastereomer. Column chromatog-
raphy on silica gel (Hexane/AcOEt 50:50), pale yellow oil. 23% (70
mg). 1H NMR (600 MHz, CDCl3) δ 1.32−1.36 (m, 1 H), 1.43−1.49
(m, 1 H), 1.68−1.76 (m, 1 H), 1.86−1.93 (m, 1 H), 1.97−2.09 (m, 2
H), 2.90−2.97 (m, 2 H), 3.15 (dd, J = 7, 14 Hz, 1 H), 3.31 (dd, J =
9.5, 5.1 Hz, 1 H), 3.86−3.97 (m, 1 H), 4.19 (bs, 1 H, OH), 5.77 (dt, J
= 10, 4 Hz, 1 H), 5.99 (d, J = 10.2 Hz, 1 H), 7.13−7.14 (m, 2 H),
7.17−7.19 (m, 1 H), 7.23−7.26 (m, 2 H). 13C NMR (125 MHz,
CDCl3) δ 20.5, 24.5, 27.3, 34.6, 40.6, 60.5, 67.5,, 129.2, 130.8, 130.9,
132.0, 133.39. FT-IR (film, cm−1) υ 700, 734, 1029, 1188, 1454, 1496,
1712, 2851, 2930, 3027, 3400. HRMS (ESI-TOF) m/z [M + Na]+
calcd for C16H20SO2Na 299.1076; found 299.1067.
(1RS*,2R*,4S*)-6e. Column chromatography on silica gel (Hexane/
1
AcOEt 50:50), pale yellow oil. 43% (96 mg). H NMR (600 MHz,
CDCl3) δ 1.34 (like q, 1 H), 2.37−2.45 (m, 2 H), 2.49−2.53 (m, 1 H),
2.90 (dd, J = 9, 14 Hz, 1 H), 3.15−3.24 (m, 2 H), 3.31−3.40 (m, 1 H),
5.04−5.12 (m, 2 H), 5.71 (ddt, J = 7, 10, 17 Hz, 1 H), 7.10−7.13 (m, 2
H), 7.16−7.19 (m, 1 H), 7.22−7.28 (m, 2 H). 13C NMR (125 MHz,
CDCl3) δ 22.6, 35.9, 38.0, 63.1, 64.4, 118.3, 127.0, 128.8, 128.9, 133.1,
137.3. FT-IR (film, cm−1) υ 702, 749, 921, 1061, 1299, 1454, 1496,
1640, 2919, 3028, 3063, 3437. ESI-MS: m/z (rel. int.): 221 [M +
H]+(100).
(1RS*,2R*,4R*)-2-(3-Propenyl)-4-methylthietane 1-Oxide
(1RS*,2R*,4R*)-7a. Column chromatography on silica gel (AcOEt),
pale yellow oil 42% (61 mg). 1H NMR (600 MHz, CDCl3) δ 1.47 (d, J
= 7.4 Hz, 3 H), 1.98 (ddd, J = 8.3, 11.9, 13.0 Hz, 1 H), 2.12−2.19 (m,
1 H), 2.43−2.48 (m, 1 H), 2.52−2.57 (m, 1 H), 3.46−3.53 (m, 2H),
5.09−5.15 (m, 2 H), 5.76 (ddt, J = 17.0, 10.2, 6.7 Hz, 1 H). 13C NMR
(125 MHz, CDCl3) δ 11.7, 25.2, 36.0, 49.4, 63.6, 118.2, 133.1. FT-IR
(film, cm−1) υ 920, 997, 1060, 1123, 1439, 1641, 2867, 2929, 2976,
3079, 3467. HRMS (ESI-TOF) m/z [M + Na]+ calcd for C7H12SONa
167.0501; found 167.0500.
(1RS*,2S*,4S*)-2-[(4-Chlorophenyl)hydroxymethyl]-4-(3-
propenyl)thietane 1-Oxide (1RS*,2S*,4S*)-7b. Mixture of diaster-
eomers dr 70:30. Column chromatography on silica gel (AcOEt),
yellow oil. 71% (192 mg). 1H NMR (600 MHz, CDCl3) δ 1.40 (q, J =
12.1 Hz, 1 H), 1.66 (q, J = 12.2 Hz, 1 H), 2.11−2.17 (m, 2 H), 2.34−
2.49 (m, 4 H), 3.08−3.17 (m, 2 H), 3.31−3.38 (m, 2 H), 4.66 (d, J =
8.5 Hz, 1 H), 5.02−5.09 (m, 5 H), 5.63−5.70 (m, 2 H), 7.17−7.24 (m,
8 H). 13C NMR (125 MHz, CDCl3) δ 17.3, 20.2, 35.7, 35.8, 61.9, 69.1,
69.2, 69.9, 73.5, 118.4, 118.5, 127.3, 127.5, 128.8, 129.0, 132.7, 132.8,
133.7, 139.3, 139.4. IR (film, cm−1) υ 757, 841, 923, 1043, 1089, 1490,
1641, 2923, 2979, 3081, 3339. HRMS (ESI-TOF) m/z [M + Na]+
calcd for C13H15ClSO2Na 293.0373; found 293.0374.
(1RS*,2R*,4S*)-2-(1-Hydroxycyclohex-2-en-1-yl)-4-(3-propenyl)-
thietane 1-Oxide (1RS*,2R*,4S*)-7c. Minor diastereomer. Column
chromatography on silica gel (Hexane/AcOEt 50:50), yellow oil. 20%
(47 mg). 1H NMR (600 MHz, CDCl3) δ 1.41−1.61 (m, overlapping s
H2O at 1.60, 2 H), 1.93−2.15 (m, overlapping s AcOEt at 2.04, 3 H),
2.46−2.62 (m, 2 H), 3.07 (ddd, J = 13.2, 11.4, 5.3 Hz, 1 H), 3.37−3.42
(m, 1 H), 3.73−3.84 (m, 1 H), 4.32 (bs, 1 H), 5.15−5.20 (m, 2 H),
5.75−5.88 (m, 2 H), 6.06−6.09 (m, 1 H). 13C NMR (125 MHz,
CDCl3) δ 18.6, 22.4, 25.2, 32.7, 36.4, 58.4, 64.1, 72.8, 118.6, 130.0,
131.1, 132.9. FT-IR (film, cm−1) υ 710, 1025, 1266, 1435, 1707, 2943,
3054, 3400. HRMS (ESI-TOF) m/z [M + Na]+ calcd for
C12H18SO2Na 249.0925; found 249.0920.
(1RS*,2R*,4S*)-2-(1-Hydroxycyclohex-2-en-1-yl)-4-(3-propenyl)-
thietane 1-Oxide (1RS*,2R*,4S*)-7c. Major diastereomer. Column
chromatography on silica gel (Hexane/AcOEt 50:50), yellow oil. 45%
(109 mg). 1H NMR (600 MHz, CDCl3) δ 1.55−1.66 (m, 1 H), 1.82−
2.17 (m, 6 H), 2.49−2.60 (m, 2 H), 3.11 (ddd, J = 13.2, 11.4, 5.4 Hz, 1
H), 3.38 (ddd, J = 9.5, 5.4, 1.3 Hz, 1 H), 3.75−3.81 (m, 1 H), 4.31 (bs,
(1RS*,2R*,4R*)/(1RS*,2R*,4S*)-6d. Mixture of diastereoisomers dr
70:30. Column chromatography on silica gel (AcOEt), yellow oil,
I
J. Org. Chem. XXXX, XXX, XXX−XXX