1700
M.-X. Wang, S.-M. Zhao / Tetrahedron: Asymmetry 13 (2002) 1695–1702
(m, 1H, -CHꢀCH2), 5.14 (d, J=18.2, 1H, trans
-CHꢀCHH), 5.09 (d, J=10.8, 1H, cis -CHꢀCHH), 3.70
(t, J=7.6, 1H, CH), 2.92–2.82 (m, 1H, CHH), 2.73–
2.53 (m, 1H, CHH); lC (CDCl3) 179.3, 136.2, 134.4,
133.5, 129.4, 128.9, 117.6, 50.7, 37.0; m/z (EI) 212
(M++2, 4), 210 (M+, 11%), 171 (35), 169 (100), 167 (26),
165 (78), 143 (12), 141 (40), 129 (70), 128 (45), 77 (35).
HRMS found: 209.0372 (M−H). C11H10ClO2 requires:
209.0375.
(HPLC analysis using a Chiralcel OJ column); wmax
(KBr)/cm−1 3400–2800 (br., COOH), 1708 (CꢀO), 1643
(CꢀC); lH (CDCl3) 10.00 (br. s, COOH), 7.23 (d,
J=8.2, 2H, ArH), 7.17 (d, J=7.9, 2H, ArH), 5.80–5.68
(m, 1H, -CHꢀCH2), 5.12 (d, J=17.6, 1H, trans
-CHꢀCHH), 5.04 (d, J=10.2, 1H, cis -CHꢀCHH), 3.64
(t, J=7.6, 1H, CH), 2.89–2.79 (m, 1H, CHH), 2.58–
2.49 (m, 1H, CHH), 2.36 (s, 3H, CH3); lC 180.1, 137.7,
135.4, 135.2 129.8, 128.3, 117.5, 51.3, 37.3, 21.4; m/z
(EI) 190 (M+, 8%), 149 (100), 145 (8), 129 (35), 128
(29), 121 (36), 115 (17), 105 (16), 93 (30), 91 (24), 77
(23). HRMS found: 189.0922 (M−H). C12H13O2
requires: 189.0921.
4.3.4. Microbial hydrolysis of 2-(4-methoxyphenyl)-4-
pentenenitrile, 1d
4.3.4.1. (R)-2-(4-Methoxyphenyl)-4-pentenamide, 2d.
Yield 47%; mp 90.5–91.4°C; [h]2D5=−84.1 (c 2.45,
CHCl3); e.e. >99.5% (HPLC analysis using a Chiralcel
OJ column); wmax (KBr)/cm−1 3410, 3340 (NH2), 1632
(CꢀO); lH (CDCl3) 7.21 (d, J=8.6, 2H, ArH), 6.87 (d,
J=8.6, 2H, ArH), 5.74–5.65 (m, 1H, -CHꢀCH2), 5.34
(br. s, 2H, CONH2), 5.04 (d, J=17.6, 1H, trans
-CHꢀCHH), 4.97 (d, J=10.1, 1H, cis -CHꢀCHH), 3.79
(s, 3H, CH3), 3.41 (t, J=7.6, 1H, CH), 2.90–2.85 (m,
1H, CHH), 2.52–2.47 (m, 1H, CHH); lC (CDCl3)
175.5, 158.7, 135.6, 131.1, 128.9, 116.6, 114.1, 55.1,
51.5, 37.0; m/z (EI) 205 (M+, 14%), 164 (85), 161 (100),
146 (79), 136 (49), 121 (26), 108 (36), 91 (34), 77 (17).
Anal. found: C, 70.03; H, 7.38; N, 6.79. C12H15NO2
requires: C, 70.22; H, 7.37; N, 6.82%.
4.3.6. Microbial hydrolysis of 2-(3-methylphenyl)-4-pent-
enenitrile, 1f
4.3.6.1. (R)-2-(3-Methylphenyl)-4-pentenamide, 2f.
Yield 49%; mp 70–70.5oC; [h]D25=−94.8 (c 2.3, CHCl3);
e.e. >99.5% (HPLC analysis using a Chiralcel OJ
column); wmax (KBr)/cm−1 3382, 3184 (NH2), 1657
(CꢀO); lH (CDCl3) 7.24–7.07 (m, 4H, ArH), 5.90 (br. s,
1H, CONHH), 5.78–5.65 (m, 1H, -CHꢀCH2), 5.49 (br.
s, 1H, CONHH), 5.05 (d, J=16.9, 1H, trans
-CHꢀCHH), 4.98 (d, J=10.1, 1H, cis -CHꢀCHH), 3.43
(t, J=7.6, 1H, CH), 2.93–2.83 (m, 1H, CHH), 2.55–
2.46 (m, 1H, CHH), 2.34 (s, 3H, CH3); lC (CDCl3)
175.4, 139.0, 138.4, 135.6, 128.5, 128.5, 128.0, 124.8,
116.6, 52.3, 36.9, 21.2; m/z (EI): 189 (M+, 3%), 171 (9),
145 (100), 130 (65), 120 (16), 105 (38), 91 (19). Anal.
found: C, 75.80; H, 7.99; N, 7.51. C12H15NO requires:
C, 76.16; H, 7.99; N, 7.40%.
4.3.4.2. (S)-2-(4-Methoxyphenyl)-4-pentenoic acid, 3d.
Yield 51%; mp 88–89.3°C; [h]2D5=+71.0 (c 2.45, CHCl3);
e.e. 87.4% (HPLC analysis using a Chiralcel OJ
column); wmax (KBr)/cm−1 3400–2800 (br., COOH),
1718 (CꢀO), 1677 (CꢀC); lH (CDCl3) 10.09 (br. s,
COOH), 7.27 (d, J=8.6, 2H, ArH), 6.90 (d, J=8.5, 2H,
ArH), 5.79–5.70 (m, 1H, -CHꢀCH2), 5.11 (d, J=17.0,
1H, trans -CHꢀCHH), 5.05 (d, J=10.2, 1H, cis
-CHꢀCHH), 3.82 (s, 3H, CH3), 3.63 (t, J=7.7, 1H,
CH), 2.88–2.78 (m, 1H, CHH), 2.58–2.51 (m, 1H,
CHH); lC (CDCl3) 179.8, 159.0, 135.0, 129.9, 129.1,
117.2, 114.1, 55.3, 50.5, 37.1; m/z (EI) 206 (M+, 14%),
165 (100), 137 (22). Anal. found: C, 69.87; H, 6.85.
C12H14O3 requires: C, 69.89; H, 6.84%.
4.3.6.2. (S)-2-(3-Methylphenyl)-4-pentenoic acid, 3f.
Yield 49%; oil; [h]D25=+68.7 (c 1.95, CHCl3); e.e.
>99.5% (HPLC analysis using a Chiralcel OD column);
wmax (KBr)/cm−1 3400–2800 (br., COOH), 1707 (CꢀO),
1643 (CꢀC); lH (CDCl3) 10.09 (br. s, COOH), 7.24–7.10
(m, 4H, ArH), 5.81–5.68 (m, 1H, -CHꢀCH2), 5.12 (d,
J=17.1, 1H, trans -CHꢀCHH), 5.04 (d, J=10.2, 1H,
cis -CHꢀCHH), 3.63 (t, J=7.6, 1H, CH), 2.88–2.79 (m,
1H, CHH), 2.58–2.48 (m, 1H, CHH), 2.36 (s, 3H,
CH3); lC (CDCl3) 180.1, 138.8, 138.3, 135.4, 129.1,
129.0, 128.7, 125.4, 117.5, 51.6, 37.4, 21.8; m/z (EI): 190
(M+, 10%), 149 (63), 145 (100), 129 (27), 128 (21), 121
(28), 115 (15), 105 (16), 93 (30), 91 (22), 77 (21). HRMS
found: 189.0923 (M−H). C12H13O2 requires: 189.0921.
4.3.5. Microbial hydrolysis of 2-(4-methylphenyl)-4-pent-
enenitrile, 1e
4.3.5.1. (R)-2-(4-Methylphenyl)-4-pentenamide, 5e.
Yield 49%; mp 85.5–87°C; [h]2D5=−75.1 (c 2.45, CHCl3);
e.e. >99.5% (HPLC analysis using a Chiralcel OJ
column); wmax (KBr)/cm−1 3387, 3189 (NH2), 1656
(CꢀO); lH (CDCl3) 7.18 (d, J=8.3, 2H, ArH), 7.14 (d,
J=8.2, 2H, ArH), 5.77–5.66 (m, 1H, -CHꢀCH2), 5.64
(br. s, 1H, CONHH), 5.41 (br. s, 1H, CONHH), 5.04
(d, J=17.0, 1H, trans -CHꢀCHH), 4.97 (d, J=10.2,
1H, cis -CHꢀCHH), 3.43 (t, J=7.5, 1H, CH), 2.93–2.84
(m, 1H, CHH), 2.55–2.48 (m, 1H, CHH), 2.32 (s, 3H,
CH3); lC (CDCl3) 175.4, 137.0, 136.0, 135.6, 129.4,
127.7, 116.6, 51.9, 36.8, 20.9; m/z (EI) 189 (M+, 5%),
171 (4), 145 (100), 130 (39), 120 (19), 105 (39), 91 (14).
Anal. found: C, 76.38; H, 7.90; N, 7.47. C12H15NO
requires: C, 76.16; H, 7.99; N, 7.40%.
4.3.7. Microbial hydrolysis of 2-(2-methylphenyl)-4-pent-
enenitrile, 1g
4.3.7.1. (R)-2-(2-Methylphenyl)-4-pentenamide, 2g.
Yield 93%; mp 86.5–88°C; [h]2D5=−1.3 (c 4.7, CHCl3);
e.e. 3.2% (HPLC analysis using a Chiralcel OD
column); wmax (KBr)/cm−1 3399, 3197 (NH2), 1652
(CꢀO); lH (CDCl3) 7.34–7.19 (m, 4H, ArH), 6.32 (br. s,
1H, CONHH), 5.81–5.70 (m, 1H, -CHꢀCH2), 5.48 (br.
s, 1H, CONHH), 5.07 (d, J=17.3, 1H, trans
-CHꢀCHH), 4.99 (d, J=10.1, 1H, cis -CHꢀCHH), 3.75
(t, J=7.5, 1H, CH), 2.96–2.87 (m, 1H, CHH), 2.58–
2.48 (m, 1H, CHH), 2.36 (s, 3H, CH3); lC (CDCl3)
175.9, 137.3, 136.1, 135.7, 130.6, 127.0, 126.4, 116.5,
48.2, 36.4, 19.6; m/z (EI): 189 (M+, 9%), 171 (8), 145
(100), 130 (55), 105 (47), 103 (30), 91 (22). Anal. found:
C, 75.94; H, 7.98; N, 7.61. C12H15NO requires: C,
76.16; H, 7.99; N, 7.40%.
4.3.5.2. (S)-2-(4-Methylphenyl)-4-pentenoic acid, 3e.
Yield 49%; oil; [h]2D5=+69.7 (c 2.55, CHCl3); e.e. 94.3%