Page 9 of 13
The Journal of Organic Chemistry
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37.8 , 134.8 , 132.4 , 130.5 , 129.5 , 128.0 , 122.7 , 121.4 (q, J = 257.5 Hz), 61.8 , 43.8 , 42.5; 19F NMR
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470 MHz, Chloroform-d) δ -55.43. HR-MS (EI) m/z: M+ Calcd. For C16
H14ClF OS 346.0406; Found
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346.0403.
(
(1S,2R,3R,4R)-3-chlorobicyclo[2.2.1]heptan-2-yl)(mesityl)sulfane 4d.14 Colorless oil, yield 89% (124.6
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mg). Eluent: ethyl acetate/petroleum ether (1:99). H NMR (500 MHz, Chloroform-d) δ 6.93 (s, 2H), 3.94
(td, J = 4.1, 1.8 Hz, 1H), 2.78 (dd, J = 3.9, 2.8 Hz, 1H), 2.52 (s, 6H), 2.47 – 2.42 (m, 1H), 2.26 (s, 3H), 2.10
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(d, J = 4.6 Hz, 1H), 1.93 (ttd, J = 12.8, 4.1, 2.2 Hz, 2H), 1.61 (dd, J = 12.5, 4.5 Hz, 1H), 1.42 (tddd, J = 10.6,
.5, 4.4, 2.1 Hz, 2H), 1.20 (ddt, J = 11.5, 4.5, 2.6 Hz, 1H).; 13C{ H} NMR (126 MHz, Chloroform-d) δ
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37.5, 135.9, 132.6, 131.1, 129.6, 128.4, 128.0, 127.8, 126.2, 116.6, 20.3.
((1S,2R,3R,4R)-3-chlorobicyclo[2.2.1]heptan-2-yl)(2,3,5,6-tetramethylphenyl)sulfane 4e. White solid,
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M.p. 55.4-57.6 ºC, yield 85% (125.0 mg). Eluent: ethyl acetate/petroleum ether (1:99). H NMR (500 MHz,
Chloroform-d) δ 6.95 (s, 1H), 3.93 (d, J = 1.9 Hz, 1H), 2.72 (dd, J = 4.0, 2.8 Hz, 1H), 2.52 (s, 6H), 2.46 –
2.42 (m, 1H), 2.24 (s, 6H), 2.07 (d, J = 4.6 Hz, 1H), 1.92 (ttd, J = 11.7, 4.2, 2.2 Hz, 2H), 1.56 (dt, J = 12.4,
.5 Hz, 1H), 1.46 – 1.38 (m, 2H), 1.18 (dddd, J = 11.6, 8.6, 4.5, 2.3 Hz, 1H).; 13C{ H} NMR (126 MHz,
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Chloroform-d) δ 137.8 , 133.2 , 131.8 , 131.1 , 65.9 , 59.4 , 43.3 , 42.3 , 34.8 , 27.8 , 20.8 , 19.9 , 17.6 .
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HR-MS (EI) m/z: M Calcd. For C17
H
23ClS 294.1209; Found 294.1207.
((1S,2R,3R,4R)-3-chlorobicyclo[2.2.1]heptan-2-yl)(2,4,6-triisopropylphenyl)sulfane 4f. White solid,
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M.p. 72.2-73.9 ºC, yield 91% (165.7 mg). Eluent: ethyl acetate/petroleum ether (1:99). H NMR (500 MHz,
Chloroform-d) δ 7.00 (s, 2H), 4.09 – 3.90 (m, 3H), 2.88 (p, J = 6.9 Hz, 1H), 2.67 (t, J = 3.3 Hz, 1H), 2.45 (d,
J = 4.4 Hz, 1H), 2.12 (d, J = 4.6 Hz, 1H), 1.99 – 1.83 (m, 2H), 1.60 (ddt, J = 12.3, 8.9, 4.4 Hz, 1H), 1.42
tddd, J = 11.2, 9.4, 4.5, 1.9 Hz, 2H), 1.28 – 1.18 (m, 19H).; 13C{ H} NMR (126 MHz, Chloroform-d) δ
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52.0 , 148.6 , 126.2 , 120.8 , 66.0 , 60.9 , 43.2 , 42.1 , 34.7 , 33.1 , 30.4 , 27.9 , 23.7 , 23.2 , 22.8 , 20.8 .
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HR-MS (EI) m/z: M Calcd. For C22
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33ClS 364.1992; Found 364.2001.
(
(
(
(
(1S,2R,3R,4R)-3-chlorobicyclo[2.2.1]heptan-2-yl)(4-fluorophenyl)sulfane 4g. Colorless oil, yield 84%
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107.5 mg). Eluent: ethyl acetate/petroleum ether (1:99). H NMR (500 MHz, Chloroform-d) δ 7.45 – 7.39
m, 2H), 7.01 (t, J = 8.7 Hz, 2H), 4.01 (td, J = 4.1, 1.8 Hz, 1H), 2.98 (dd, J = 3.9, 2.8 Hz, 1H), 2.51 – 2.45
m, 1H), 2.25 (d, J = 4.6 Hz, 1H), 1.98 (dddd, J = 13.3, 9.2, 4.5, 2.4 Hz, 1H), 1.81 (dp, J = 10.7, 1.9 Hz, 1H),
.68 (tt, J = 12.5, 4.6 Hz, 1H), 1.50 – 1.40 (m, 2H), 1.34 (dddd, J = 11.9, 9.2, 4.6, 2.3 Hz, 1H); 13C{ H}
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NMR (126 MHz, Chloroform-d) δ 161.2 (d, J = 247.4 Hz), 132.8 (d, J = 8.1 Hz), 128.9 , 115.0 (d, J = 21.8
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Hz), 66.2 , 59.2 , 43.3 , 42.5 , 34.7 , 27.8 , 20.7; F NMR (470 MHz, Chloroform-d) δ -113.56. HR-MS (EI)
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14ClFS 256.0489; Found 256.0493.
(
(1S,2R,3R,4R)-3-chlorobicyclo[2.2.1]heptan-2-yl)(4-chlorophenyl)sulfane 4h.16 Colorless oil, yield 81%
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(110.2 mg). Eluent: ethyl acetate/petroleum ether (1:99). H NMR (500 MHz, Chloroform-d) δ 7.32 (d, J =
.5 Hz, 2H), 7.26 (d, J = 8.6 Hz, 2H), 4.01 (td, J = 4.1, 1.8 Hz, 1H), 3.04 (dd, J = 3.9, 2.7 Hz, 1H), 2.49 (q, J
3.7 Hz, 1H), 2.26 (d, J = 4.6 Hz, 1H), 1.99 (dddd, J = 13.2, 9.1, 4.5, 2.4 Hz, 1H), 1.80 (dp, J = 10.5, 1.9
Hz, 1H), 1.70 (tt, J = 12.5, 4.6 Hz, 1H), 1.51 – 1.41 (m, 2H), 1.37 (dddd, J = 11.8, 9.1, 4.6, 2.3 Hz, 1H).;
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C{ H} NMR (126 MHz, Chloroform-d) δ 132.7 , 131.7 , 131.0 , 128.0 , 66.1 , 58.3 , 43.2 , 42.6 , 34.8 ,
7.8 , 20.7.
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(4-bromophenyl)((1S,2R,3R,4R)-3-chlorobicyclo[2.2.1]heptan-2-yl)sulfane 4i. Colorless oil, yield 83%
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(131.1 mg). Eluent: ethyl acetate/petroleum ether (1:99). H NMR (500 MHz, Chloroform-d) δ 7.44 – 7.39
(m, 2H), 7.28 – 7.23 (m, 2H), 4.01 (td, J = 4.1, 1.8 Hz, 1H), 3.08 – 3.02 (m, 1H), 2.50 (d, J = 4.4 Hz, 1H),
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.27 (d, J = 4.7 Hz, 1H), 2.00 (dddd, J = 13.2, 9.1, 4.6, 2.4 Hz, 1H), 1.81 (dp, J = 10.7, 2.0 Hz, 1H), 1.70 (tt,
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J = 12.4, 4.6 Hz, 1H), 1.53 – 1.44 (m, 2H), 1.38 (dddd, J = 11.7, 9.0, 4.5, 2.2 Hz, 1H).; C{ H} NMR (126
MHz, Chloroform-d) δ 137.5, 135.9, 132.6, 131.1, 129.6, 128.4, 128.0, 127.8, 126.2, 116.6, 20.3. HR-MS
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