Molecules 2016, 21, 805
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0.97 (s, 5H) and 0.98 (s, 1H), 1.32 (s, 7.5 H) and 1.35 (s, 1.5H), 2.67–2.95 (m, 2H), 3.14–3.35 (m, 2H),
3.56–3.92 (m, 2H), 4.05 (br, 0.17H) and 4.11 (br, 0.83H), 4.51 (br, 0.83H) and 4.89 (d, J = 8.6, 0.17H), 6.71
(d, 0.36H) and 6.75 (d, 1.64H), 7.01 (overlapping d, 2H), 7.61 (m, 2H), 7.67 (m, 1H), 7.83 (d, 0.36H)
and 7.90 (d, 1.64H), ppm.13C-NMR: δ ´4.45, 18.2, 25.7, 28.2, 35.0 (s), 37.5 (a), 55.3 (s), 55.9 (a), 59.9 (s),
60.4 (a) 65.7 (a), 68.1 (s), 79.7, 120.0 (a), 120.1 (s), 127.8 (a), 127.9 (s), 129.4, 130.1, 130.4, 134.1, 139.1,
154.4 (s), 155.7 (a) ppm. ESI-MS: m/z 558.2 [M + Na]+, 574.2 [M + K]+. 5f (syn isomer): White solid, mp
25
159–161 ˝C; rαsD
´
6.7 (c 1.5, CHCl3), IR: 3369, 1747, 1705, 1609, 1512 cm´1; 1H-NMR:
δ 0.16 (s, 6H),
0.96 (s, 9H), 1.30 (s, 9H) 1.80 (s, 3H), 2.45 (m, 1H), 2.84 (m, 1H), 3.43 (m, 2H), 4.04 (br, 1H), 4.48 (br,
1H), 5.29–5.34 (m, 1H) 6.73 (d, J = 8.3 Hz, 2H), 6.98 (d, J = 8.3 Hz, 2H), 7.56 (t, 2H), 7.65 (m, 1H), 7.88
(d, J = 7.5 Hz, 2H) ppm; 13C-NMR: δ ´4.5, 18.2, 20.6, 25.6, 28.1, 35.9, 53.5, 56.6, 69.7, 79.9, 120.1, 128.2,
129.0, 129.3, 129.9, 133.8, 139.3, 154.4, 155.3, 169.8 ppm; ESI-MS: m/z 600 [M + Na]+, 616.2 [M + K]+.
6f: white solid, mp 51–53 ˝C; ee = 80% (by HPLC); rαs2D5 + 1.2 (c 1, CHCl3); IR 2957, 2930, 2858, 1702,
1610, 1510 cm´1; 1H-NMR:
δ 0.19 (s, 6H), 0.98 (s, 9H), 1.41 (s, 9H), 2.76 (m, 2H), 4.36 (br, 1H), 4.47 (br,
1H), 5.06 (dt, J = 10.3, 1.2 Hz, 1H), 5.09 (dt, J = 17.4, 1.2 Hz, 1H), 5.78 (ddd, J = 10.3, 17.4, 5.5 Hz, 1H),
6.76 (d, 2H), 7.02 (d, 2H) ppm; 13C-NMR: δ ´4.8, 18.0, 25.7, 28.4, 40.4, 79.0, 114.5, 119.9, 130.0, 130.1,
130.4, 138.2, 154.2 ppm. ESI-MS: m/z 400 [M + Na]+. Anal. Calcd for C21H35NO3Si: C, 66.80; H, 9.34; N,
3.71. Found: C, 66.88; H, 9.26; N, 3.73.
1
(3S)-3-(tert-Butoxycarbonylamino)-4-[4-(hydroxy)phenyl]-1-butene (6f ): 81% from 5f by method B. White
26
˝
solid, mp 82–84 C; rαsD +21.5 (c 1.5, CHCl3); IR = 3339, 1683, 1615, 1516 cm´1; 1H-NMR:
δ 1.41 (s, 9H),
2.75 (m, 2H), 4.35 (br, 1H), 4.50 (br, 1H), 5.07 (dd, J = 10.3, 1.2 Hz, 1H), 5.10 (dd, J = 17.4, 1.2 Hz, 1H),
5.60 (br, 1H), 5.78 (ddd, J = 17.4, 10.3, 5.5 Hz, 1H), 6.75, (d, 2H), 7.01 (d, 2H) ppm; 13C-NMR:
δ 28.4, 40.6,
53.7, 79.7, 114.7, 115.3, 129.0, 130.6, 138.1, 154.6, 155.5 ppm; ESI-MS: m/z 286.1 [M + Na]+, 302 [M + K]+.
Anal. Calcd for C15H21NO3: C, 68.42; H, 8.04; N, 5.32; O, 18.23; Found: C, 68.41; H, 8.10; N, 5.24.
(2S)-1-(tert-Butoxycarbonyl)-2-vinylpyrrolidine (6g) [35]: 84% via alcohol 4g and acetate 5g (method´B1).
4g: 3:2 mixture of syn (s) and anti (a) diastereoisomers. Pale yellow oil; IR: 3493, 1687, 1305, 1148 cm
;
1H-NMR (d6-DMSO, 80 ˝C):
δ
1.38 (s, 5.4H), 1.39 (s, 3.6H), 1.66–1.92 (m, 2H), 3.08–3.40 (m, 2H), 3.66
(m, 0.6H), 3.80 (m, 0.4H), 4.25 (br, 1H), 4.84 (d, J = 6.0 Hz, 0.4H), 4.91 (d, J = 6.5 Hz, 0.6H), 7.63 (m,
2H), 7.70 (m, 1H), 7.89 (m, 2H) ppm; 13C-NMR (d6-DMSO, 80 ˝C):
22.9 (a), 24.7 (s), 26.2 (s), 27.6 (a),
δ
27.8 (s), 30.0 (a), 46.2 (s), 46.7 (a), 58.8 (a), 59.8 (s), 60.4 (a), 60.8 (s), 65.6 (s), 66.8 (a), 78.1 (s), 78.3 (a),
126.3 (a), 127.1 (s), 128.6 (s), 128.8 (a), 132.8 (a), 132.9 (s), 140.26 (a), 140.27 (s), 153.5 (s), 153.8 (a) ppm;
ESI-MS: m/z 378 [M + Na]+, 394 [M + K]+. 5g (syn isomer): white solid, mp 140–143 ˝C; rαs2D5 –33.1 (c
1.25, CHCl3) IR: 1747, 1692, 1520 cm´1; 1H-NMR (d6-DMSO, 80 ˝C):
δ 1.38 (s, 9H), 1.67–1.87 (m, 4H),
1.76 (s, 3H), 3.04 (m, 1H), 3.31 (m, 1H), 3.60, 3.65 (part AB of an ABX system, J = 4.1, 7.9, 15.0 Hz, 2H),
3.84 (br, 1H), 5.52 (m, 0.5H), 5.73 (m, 1H), 7.65 (m, 2H), 7.74 (m, 1H), 7.87 (m, 2H) ppm; 13C-NMR
(d6-DMSO, 80 ˝C):
δ
19.5, 22.4, 24.7, 27.2, 45.7, 55.6, 58.8, 66.9, 78.0, 127.2, 128.2, 133.0, 139.1, 153.2,
25
168.1 ppm; ESI-MS: m/z 378 [M + Na]+, 394 [M + K]+. 6g: oil, ee > 99.5% (by GLC); rαsD
´15 (c 0.75,
]
´
15.7 (c 0.55, CHCl3]; 1H-NMR (rotamers):
δ 1.43 (s, 9H), 1.69 (m, 1H), 1.77–1.79 (m,
2H), 2.02 (m, 1H), 3.38 (m, 2H), 4.27 (br, 1H), 5.04 (m, 2H), 5.73 (m, 1H) ppm; 13C-NMR (rotamers):
δ
22.6 and 23.2, 28.3, 31.4 and 31.8, 46.0 and 46.4, 59.0, 79.0, 113.6, 138.8 and 139.0, 154.8 ppm; ESI-MS:
m/z 220 [M + Na ]+.
(4S)-4-(tert-Butoxycarbonylamino)-5-phenyl-1-butene (6h): 8:2 mixture of E and Z isomers, 60% via alcohol
4h and acetate 5h (method B). 4h: mixture of 4 diastereoisomers in approximately 1:1:3:3 ratio. White
1
solid; IR: 3372, 1704, 1297, 1142 cm´1; H-NMR:
δ [1.03, 1.06, 1.20 (d, 3H)], [1.23, 1.29, 1.31, 1.36
(s, 9H)], 2.75–3.15 (multiplets, 2H, CH2), 3.20–3.30 (m, 1H, CH(CH3)), [3.70, 3.85, 3.98 (multiplets,
1H, CH(NH))], [3.80, 4.06, 4.15 (multiplets, 1H, CH(OH))], [4.38, 4.50 (br, 1H, OH)], [4.85, 4.99, 5.05
(d, 1H, NH)], 7.20–7.30 (m, 5H), 7.53–7.73 (m, 3H), 7.80–7.91 (m, 2H). 13C-NMR:
δ [7.1, 11.0, 11.4, 11.7
(CH3CH)], [28.0, 28.17, 28.22, 28.25 (tBu)], [34.2, 36.8, 38.9, 39.8 (CH2)], [52.4, 52.7, 53.0, 54.8 (CHNH)],
[60.6, 63.1, 63.4, 63.6 (CHSO2Ph)], [69.1, 69.4, 70.0, 72.3 (CHOH)], [79.4, 79.7, 79.8 (tBu)], [126.4–137.7