Arkivoc 2017, v, 0-0
Olszewska, B. et al.
1H, J 13.6, 7.4, CH2C6H5), 3.03 (dt, 1H, J 9.4, 2.6, H-6’), 3.08 (dd, 1H, J 13.4, 7.4, CH2C6H5), 3.08–3.12 (m, 1H, H-
2), 3.67 (s, 3H, OCH3), 3.88 (t, 1H, J 7.5, CHC=O), 5.03 (dd, 1H, J 10.1, 1.9, CHCH2), 5.15 (dd, 1H, J 17.2, 1.9,
CHCH2), 5.39 (ddd, 1H, J 17.2, 10.1, 8.9, CHCH2), 7.19–7.23 (m, 2H, C6H5), Rf 7.26–7.31 (m, 3H, C6H5); δC (150
MHz, CDCl3) δ 23.1, 23.9 (C-4, C-5), 29.1 (C-3), 39.0 (CH2C6H5), 46.7 (COOCH3), 64.2 (C-6), 64.9 (C-2), 68.3
(CHC=O), 116.6 (CHCH2), 126.2, 128.9, 129.0, 129.6, 131.0, 132.7 (C6H5), 141.6 (CHCH2), 167.9 (C=O); HRMS
(EI): M+, found 273.17269. C17H23NO2 requires 273.17288.
[]2D0
(S)-Methyl 3-phenyl-2-((S)-2-vinylpiperidin-1-yl)propanoate (7c). (Hexane/EtOAc, 3 : 1) 0.70;
-48.8 (c
0.5, CHCl3); δH (600 MHz, CDCl3) 1.30-1.79 (m, 6H, 2H-3, 2H-4, 2H-5), 2.47 (dt, 1H, J 11.3, 2.8, H-6’), 2.96 (dt,
1H, J 11.3, 2.8, H-6’), 2.99 (dd, 1H, J 13.1, 10.3, CH2C6H5), 3.07–3.12 (m, 3H, CH2C6H5, H-2), 3.59 (s, 3H, OCH3),
3.91 (dd, 1H, J 10.3, 4.1, CHC=O), 5.18 (dd, 1H, J 10.2, 1.8, CHCH2), 5.28 (dd,1H, J 17.3, 1.8, CHCH2), 5.89 (ddd,
1H, J 17.3, 10.2, 9.0, CHCH2), 7.14–7,20 (m, 3H, C6H5), 7.23–7.28 (m, 2H, C6H5); δC (150 MHz, CDCl3) δ 23.1,
23.9 (C-4, C-5), 30.5 (C-3), 38.9 (CH2C6H5), 47.2 (COOCH3), 64.3 (C-6), 66.2 (C-2), 68.3 (CHC=O), 116.3 (CHCH2),
126.2, 128.4, 129.0, 129.5, 131.0, 132.7 (C6H5), 141.5 (CHCH2), 167.8 (C=O); HRMS (EI): M+, found 273.17254.
C17H23NO2 requires 273.17288.
(S)-Methyl 3-phenyl-2-((R)/(S)-2-vinylpyrrolidin-1-yl)propanoate (6d/7d). Colorless oil, 99% (THF, 25 °C), 98%
(CH2Cl2, 25 °C) yield; max (liquid film) 3056, 3025, 2942, 2870, 1739, 1654, 1603, 1578, 1499, 1442, 1204, 1125,
751, 701 cm-1; MS-EI m/z: 260 (MH+, 100).
[]20
(S)-Methyl 3-phenyl-2-((R)-2-vinylpyrrolidin-1-yl)propanoate (6d). (Hexane/EtOAc, 3 : 1) 0.81;
-16.21 (c
D
0.5, CHCl3); δH (600 MHz, CDCl3) 1.25-1.78 (m, 4H, H-3, H-4), 2.13 (ddd, 1H, J 11.7, 9.4, 2.5, H-5), 2.82 (dd, 1H, J
13.4, 7.4, CH2C6H5), 3.00 (ddd, 1H, J 9.4, 7.5, 3.0, H-5’), 3.05 (dd, 1H, J 13.4, 7.4, CH2C6H5), 3.05–3.09 (m, 1H, H-
2), 3.64 (s, 3H, OCH3), 3.85 (t, 1H, J 7.5, CHC=O), 4.99 (dd, 1H, J 10.1, 1.9, CHCH2), 5.12 (dd, 1H, J 17.5, 1.9,
CHCH2), 5.35 (ddd, 1H, J 17.5, 10.1, 8.8, CHCH2), 7.15–7.20 (m, 2H, C6H5), 7.23–7.28 (m, 3H, C6H5); δC (150
MHz, CDCl3) δ 23.9 (C-4), 29.1 (C-3), 38.9 (CH2C6H5), 46.7 (COOCH3), 50.9 (C-5), 62.5 (C-2), 68.3 (CHC=O), 116.6
(CHCH2), 126.4, 128.3, 129.0, 129.2, 131.0, 140.7 (C6H5), 132.7 (CHCH2), 167.9 (C=O); HRMS (EI): M+, found
259.15708. C16H21NO2 requires 259.15723.
[]20
(S)-Methyl 3-phenyl-2-((S)-2-vinylpyrrolidin-1-yl)propanoate (7d). (Hexane/EtOAc, 3 : 1) 0.65;
-8.13 (c 1,
D
CHCl3); δH (600 MHz, CDCl3) 1.46-1.74 (m, 4H, H-3, H-4), 2.44 (ddd, 1H, J 2.8, 9.8, 7.5, H-5), 2.91 (ddd, 1H, J 4.0,
11.9, 9.8, H-5), 2.96 (dd, 1H, J 13.1, 10.3, CH2C6H5), 3.03-3.08 (m, 2H, H-2, CH2C6H5), 3.56 (s, 3H, OCH3), 3.88
(dd, 1H, J 10.3, 4.1, CHC=O), 5.15 (dd, 1H, J 10.1, 1.8, CHCH2), 5.24 (dd, 1H, J 17.5, 1.8, CHCH2), 5.86 (ddd, 1H, J
17.5, 10.1, 9.0, CHCH2), 7.12-7.17 (m, 1H, C6H5), 7.20-7.24 (m, 1H, C6H5), 7.30-7.44 (m, 3H, C6H5); δC (150 MHz,
CDCl3) 23.0 (C-4), 30.6 (C-3), 37.7 (CH2C6H5), 46.7 (COOCH3), 50.9 (C-5), 65.1 (C-2), 65.7 (CHC=O), 116.6
(CHCH2), 128.3, 128.9, 129.0, 129.6, 131.0, 138.8 (C6H5), 132.6 (CHCH2), 167.8 (C=O); HRMS (EI): M+, found
259.15711. C16H21NO2 requires 259.15723.
(S)-Methyl 2-((R)/(S)-2-vinylpyrrolidin-1-yl)propanoate (6e/7e). Colorless oil, 97% (THF, 55 °C), 98% (CH2Cl2,
35 °C) yield; max (liquid film) 3053, 2965, 2873, 1733, 1651, 1261, 1192 cm-1; MS-EI m/z: 184 (MH+, 100);
HRMS (EI): M+, found 183.12591. C10H17NO2 requires 183.12593.
(S)-Methyl 2-((R)-2-vinylpyrrolidin-1-yl)propanoate (6e). δH (600 MHz, CDCl3) 1.26 (d, 3H, J 7.2, CHCH3), 1.45-
1.70 (m, 4H, H-3, H-4), 2.73 (q, 1H, J 8.5, H-5), 2.94-2.97 (m, 1H, H-5), 3.16 (q, 1H, J 7.9, H-2), 3.51 (q, 1H, J 7.2,
CHCH3), 3.59 (s, 3H, COOCH3), 4.94 (dd, 1H, J 10.0, 1.9, CH=CH2), 5.03 (dd, 1H, J 18.5, 1.9, CHCH2), 5.56 (ddd,
1H, J 18.2, 10.0, 8.3, CHCH2); δC (150 MHz, CDCl3) δ 17.3 (CHCH3), 22.8 (C-4), 32.2 (C-3), 46.8 (C-5), 51.0
(COOCH3), 55.8 (CHCH3), 65.8 (C-2), 116.4 (CHCH2), 140.9 (CHCH2), 174.1 (C=O).
(S)-Methyl 2-((S)-2-vinylpyrrolidin-1-yl)propanoate (7e). δH (600 MHz, CDCl3) 1.18 (d, 3H, J 6.9, CHCH3), 1.45-
1.70 (m, 4H, H-3, H-4), 2.43 (q, 1H, J 8.5, H-5), 2.97-2.99 (m, 1H, H-5), 3.03 (q, 1H, J 7.8, H-2), 3.54 (q, 1H, J 6.9,
CHCH3), 3.60 (s, 3H, COOCH3), 4.99 (dd, 1H, J 10.0, 1.9, CH=CH2), 5.06 (dd, 1H, J 18.5, 1.9, CHCH2), 5.64 (ddd,
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