804
S. H. Kwak et al. / Tetrahedron: Asymmetry 21 (2010) 800–804
J = 8.0 Hz),4.96(d, 1H, J = 6.8 Hz), 4.55 (qn, 1H, J = 6.9 Hz), 2.36 (s, 3H),
1.42 (d, 3H, 6.9 Hz); 13C NMR (75 MHz, CDCl3) d 146.2, 143.6, 137.6,
129.8 (q, JF–C = 32.3 Hz), 129.6, 127.3, 126.8, 125.6 (q, JF–C = 3.4 Hz),
124.2 (q, JF–C = 271.2 Hz), 53.5, 23.7, 21.5; EIMS (70 eV) m/z (rel inten-
4.2.1.14. (S)-1-(2-Benzothienyl)-N-tosylethanamine 6o. Yield = 91%; 1H
NMR (300 MHz, CDCl3) d 7.71–7.67 (m, 3H), 7.62–7.58 (m, 1H), 7.33–7.23
(m, 2H), 7.15 (d, 2H, J = 8.1 Hz), 6.95 (s, 1H), 4.88–4.79 (m, 2H), 2.32 (s, 3H),
1.59 (d, 3H, J = 6.4 Hz); 13C NMR (75 MHz, CDCl3) d 146.4, 143.4, 139.3,
139.2, 137.5, 129.4, 127.1, 124.4, 123.5, 122.3, 121.2, 50.0, 23.6, 21.4; EIMS
(70 eV) m/z (rel intensity) 331 (M+, 46), 316 (20), 175 (100), 160 (49), 91
sity) 343 (M+, 1), 328 (100), 188 (23), 155 (61), 91 (69); ½a 2D0
¼ ꢂ48:1
ꢁ
(c 0.58, CHCl3); HPLC (Chiralcel OD-H, i-PrOH/hexane 10/90, 0.8 mL/
min) t1 = 11.7 min (R), t2 = 12.8 min (S); ee = 96%.
(53); ½a 2D0
¼ ꢂ103:5 (c0.72, CHCl3); HPLC (Chiralpak AD-H, i-PrOH/hexane
ꢁ
20/80, 0.8 mL/min) t1 = 16.7 min (S), t2 = 20.8 min (R); ee = 97%.
4.2.1.9. (S)-1-(2-Naphthyl)-N-tosylethanamine 6j4,17
. Yield = 94%;
4.2.1.15. (S)-1-Cyclopropyl-N-tosylethanamine 6p4b
. Yield = 92%;
1H NMR (300 MHz, CDCl3) d 7.77–7.74 (m, 1H), 7.68–7.65 (m, 2H),
7.57 (d, 2H, J = 8.2 Hz), 7.46–7.41 (m, 3H), 7.20 (dd, 1H, J = 8.5 and
1.4 Hz), 7.03 (d, 2H, J = 8.0 Hz), 4.91 (d, 1H, J = 6.8 Hz), 4.63 (qn,
1H, J = 6.8 Hz), 2.25 (s, 3H), 1.51 (d, 3H, J = 6.8 Hz); 13C NMR
(75 MHz, CDCl3) d 143.1, 139.1, 137.5, 133.1, 132.7, 129.3, 128.4,
127.8, 127.5, 127.1, 126.2, 126.0, 125.1, 124.1, 53.8, 23.4, 21.3; EIMS
(70 eV) m/z (rel intensity) 325 (M+, 58), 310 (100), 170 (57), 155
1H NMR (300 MHz, CDCl3) d 7.78–7.75 (m, 2H), 7.29 (d, 2H,
J = 8.2 Hz), 4.69 (d, 1H, 6.3 Hz), 2.71–2.60 (m, 1H), 2.43 (s, 3H), 1.14
(d, 3H, J = 6.6 Hz), 0.81–0.70 (m, 1H), 0.49–0.28 (m, 2H), 0.17–0.09
(m, 1H), 0.04–0.04 (m, 1H); 13C NMR (75 MHz, CDCl3) d 143.1,
138.2, 129.5, 127.1, 54.7, 21.5, 21.2, 17.9, 3.6, 3.2; EIMS (70 eV) m/z
(rel intensity) 239 (M+, 3), 224 (69), 198 (15), 155 (71), 91 (100);
½
a 2D0
ꢁ
¼ þ7:5 (c 0.99, CHCl3); HPLC (Chiralpak AD-H, i-PrOH/hexane
(57), 91 (35); ½a D20
ꢁ
¼ ꢂ72:0 (c 0.5, CHCl3); HPLC (Chiralcel OD-H, i-
20/80, 0.8 mL/min) t1 = 9.8 min (S), t2 = 11.4 min (R); ee = 67%.
PrOH/hexane 15/85, 1.0 mL/min) t1 = 11.2 min (R), t2 = 12.0 min
(S); ee = 96%.
Acknowledgments
4.2.1.10. (S)-1-Phenyl)-N-tosylpropylamine 6k4b
. Yield = 86%;
This work was supported by grants for Industrial Technology
Development Programs from the Ministry of Knowledge Economy
of Korea (TS072-03) and the Korea Research Institute of Chemical
Technology (BS.F-0801).
1H NMR (300 MHz, CDCl3) d 7.55–7.51 (m, 2H), 7.17–7.09 (m,
5H), 7.03–6.98 (m, 2H), 4.96 (d, 1H, J = 7.3 Hz), 4.19 (q, 1H,
J = 7.0 Hz), 2.35 (s, 3H), 1.86–1.66 (m, 2H), 0.78 (t, 3H, J = 7.3 Hz);
13C NMR (75 MHz, CDCl3) d 142.9, 140.7, 137.7, 129.3, 128.4,
127.3, 127.0, 126.6, 59.8, 30.6, 21.4, 10.4; EIMS (70 eV) m/z (rel
References
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¼ ꢂ52:4
ꢁ
(c 0.72, CHCl3); HPLC (Chiralcel OD-H, i-PrOH/hexane 15/85,
0.7 mL/min) t1 = 9.0 min (R), t2 = 10.3 min (S); ee = 95%.
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1H NMR (300 MHz, CDCl3) d 7.70–7.67 (m, 2H), 7.25–7.22 (m,
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(70 eV) m/z (rel intensity) 265 (M+, 3), 250 (13), 155 (37), 110
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ꢁ
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J = 8.5 Hz), 4.68 (qn, 1H, J = 7.1 Hz), 2.24 (s, 3H), 1.55 (d, 3H,
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PrOH/hexane 20/80, 0.8 mL/min) t1 = 11.9 min (R), t2 = 13.5 min (S);
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4.2.1.13. (S)-1-(2-Thienyl)-N-tosylethanamine 6n. Yield = 97%;
1H NMR (300 MHz, CDCl3) d 7.72–7.69 (m, 2H), 7.27–7.24 (m,
2H), 7.12 (dd, 1H, J = 5.1 and 1.1 Hz), 6.84–6.82 (m, 1H), 6.77–
6.76 (m, 1H), 4.80–4.70 (m, 2H), 2.41 (s, 3H), 1.54 (d, 3H,
J = 6.4 Hz); 13C NMR (75 MHz, CDCl3) d 143.8, 141.1, 135.4, 127.3,
124.9, 124.4, 122.5, 122.1, 47.0, 21.7, 19.3; EIMS (70 eV) m/z (rel
intensity) 281 (M+, 3), 155 (27), 126 (100), 111 (27), 91 (46);
½
a 2D0
ꢁ
¼ ꢂ68:6 (c 0.61, CHCl3); HPLC (Chiralcel OD-H, i-PrOH/hexane
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13/87, 0.6 mL/min) t1 = 14.8 min (R), t2 = 16.0 min (S); ee = 97%.