2846
K. V. Belyaeva et al.
PAPER
was stirred at 20–25 °C for 24 h. Column chromatography afforded
compound 4a as an orange oil; yield: 0.146 g (42%). Initial pyrrole-
2-carbaldehyde 3a was recovered (0.030 g, conversion was 75%).
IR (microlayer): 1023, 1057, 1078, 1116 (C–O–C), 1641 (C=C),
2216 cm–1 (CN).
1H NMR (400.13 MHz, CDCl3): d = 3.49 (s, 3 H, NCH3), 3.75 (s, 3
H, OCH3), 5.06 (s, 1 H, H11), 5.14 (d, 3JHB,HX = 15.7 Hz, 1 H, HB),
5.37 (d, 3JHA,HX = 8.8 Hz, 1 H, HA), 5.98 (s, 1 H, H6), 6.14 (d, 1 H,
H3¢), 6.19 (d, 3JH4¢,H3¢ = 3.9 Hz, 1 H, H4¢), 6.87 (s, 1 H, H5), 7.09 (s,
1 H, H4), 7.11 (2 d, 3JHB,HX = 15.7 Hz, 3JHA,HX = 8.8 Hz, 1 H, HX),
6.76–6.89, 7.10–7.40 (m, 14 H, 3 Ph).
13C NMR (100.62 MHz, CDCl3): d = 33.0 (NCH3), 34.7 (C6), 55.1
(OCH3), 83.5 (C11), 101.4 (C7), 109.2 (N1¢-CHAHB), 111.2 (C3¢),
112.2 (C4¢), 113.6 (C5¢-m-CPh), 115.1 (13-CN), 117.0 (12-CN),
121.7 (C5), 125.5 (C2¢), 126.4 (C8-o-CPh), 127.6 (C4), 128.1 (C10-
o-CPh; C8-p-CPh), 128.6 (C10-m-CPh), 128.8 (C8-m-CPh), 130.0
(C10-p-CPh, C5¢-o-CPh), 130.6 (C5¢-i-CPh), 130.7 (C5¢), 131.2 (N1¢-
CHX), 131.5 (C10-i-CPh), 131.7 (C8-i-CPh), 144.7 (C2), 158.5 (C5¢-
p-CPh), 162.2 (C8), 168.3 (C10).
IR (microlayer): 1027, 1076, 1113, 1126 (C–O–C), 1643 (C=C),
2219 cm–1 (CN).
1H NMR (400.13 MHz, CDCl3): d = 3.47 (s, 3 H, NCH3), 4.91 (d,
3JHA,HX = 8.8 Hz, 1 H, HA), 5.12 (s, 1 H, H11), 5.20 (d,
3JHB,HX = 15.7 Hz, 1 H, HB), 5.89 (s, 1 H, H6), 6.00 (2 d,
3JH3¢,H4¢ = 3.7 Hz, 4JH3¢,H5¢ = 1.7 Hz,
1
H, H3¢), 6.16 (2 d,
3JH4¢,H5¢ = 3.1 Hz, 1 H, H4¢), 6.90 (s, 1 H, H5), 7.04 (2 d, 1 H, H5¢),
7.09 (2 d, 3JHB,HX = 15.7 Hz, 3JHA,HX = 8.8 Hz, 1 H, HX), 7.11 (s, 1
H, H4), 7.10–7.30 (m, 10 H, 2 Ph).
13C NMR (100.62 MHz, CDCl3): d = 33.1 (NCH3), 34.6 (C6), 83.7
(C11), 100.8 (C7), 101.1 (N1¢-CHAHB), 109.9 (C4¢), 111.1 (C3¢),
115.0 (13-CN), 116.8 (12-CN), 118.7 (C5¢), 122.1 (C5), 126.3 (C8-
o-CPh), 126.8 (C2¢), 127.8 (C4), 128.2 (C8-p-CPh, C10-o-CPh), 128.7
(C10-m-CPh), 128.8 (C8-m-CPh), 130.0 (N1¢-CHX), 130.8 (C10-p-
CPh), 131.4 (C10-i-CPh), 131.7 (C8-i-CPh), 143.9 (C2), 162.5 (C8),
168.2 (C10).
Anal. Calcd for C36H29N5O2: C, 76.71; H, 5.19; N, 12.42. Found: C,
76.58; H, 5.19; N, 12.01.
(Z)-3-{[(Z)-2-Cyano-1-phenylvinyl]oxy}-2-[(1-methyl-1H-imi-
dazol-2-yl)(1-vinyl-4,5,6,7-tetrahydro-1H-indol-2-yl)methyl]-3-
phenylprop-2-enenitrile (4d)
Following the typical procedure for 4a using acetylene 2 (0.254 g,
2 mmol), pyrrole-2-carbaldehyde 3d (0.175 g, 1 mmol), and 1-meth-
yl-1H-imidazole (1, 0.082 g, 1 mmol) in MeCN (0.2 mL) at 20–25
°C for 24 h) gave 4d as a brown oil; yield: 0.030 g (14%). Initial
pyrrole-2-carbaldehyde 3d was recovered (0.102 g, conversion was
42%).
15N NMR (40.55 MHz, CDCl3): d = –222.9 (N1), –208.9 (N1¢),
–118.7 (N3), –112.9 (13-CN).
Anal. Calcd for C29H23N5O: C, 76.13; H, 5.07; N, 15.31. Found: C,
76.27; H, 5.03; N, 15.45.
(Z)-3-{[(Z)-2-Cyano-1-phenylvinyl]oxy}-2-[(1-methyl-1H-imi-
dazol-2-yl)(5-phenyl-1-vinyl-1H-pyrrol-2-yl)methyl]-3-phenyl-
prop-2-enenitrile (4b)
Following the typical procedure for 4a using acetylene 2 (0.254 g,
2 mmol), pyrrole-2-carbaldehyde 3b (0.197 g, 1 mmol), and 1-me-
thyl-1H-imidazole (1, 0.082 g, 1 mmol) in MeCN (0.5 mL) at 20–
25 °C for 24 h gave 4b as a dark orange oil; yield: 0.119 g (33%).
Initial pyrrole-2-carbaldehyde 3b was recovered (0.067 g, conver-
sion was 66%).
IR (microlayer): 1028, 1060, 1077, 1112, 1131 (C–O–C), 1650
(C=C), 2219 cm–1 (CN).
1H NMR (400.13 MHz, CDCl3): d = 1.76 (m, 4 H, H5¢, H6¢), 2.51
(m, 2 H, H4¢), 2.68 (m, 2 H, H7¢), 3.51 (s, 3 H, NCH3), 5.04 (d,
3JHB,HX = 15.7 Hz, 1 H, HB), 5.07 (s, 1 H, H11), 5.12 (d,
3JHA,HX = 8.8 Hz, 1 H, HA), 5.86 (s, 1 H, H3¢), 5.88 (s, 1 H, H6), 6.86
IR (microlayer): 1028, 1042, 1076, 1114 (C–O–C), 1643 (C=C),
2219 cm–1 (CN).
3
3
(s, 1 H, H5), 6.88 (2 d, JHB,HX = 15.7 Hz, JHA,HX = 8.8 Hz, 1 H,
HX), 7.10 (s, 1 H, H4), 7.10–7.33 (m, 10 H, 2 Ph).
1H NMR (400.13 MHz, CDCl3): d = 3.50 (s, 3 H, NCH3), 5.06 (s, 1
H, H11), 5.14 (d, 3JHB,HX = 15.7 Hz, 1 H, HB), 5.39 (d, 3JHA,HX = 8.8
Hz, 1 H, HA), 5.99 (s, 1 H, H6), 6.18 (d, 1 H, H3¢), 6.28 (d,
3JH4¢,H3¢ = 3.9 Hz, 1 H, H4¢), 6.89 (s, 1 H, H5), 7.08 (2 d,
13C NMR (100.62 MHz, CDCl3): d = 22.8 (C5¢, C6¢), 23.6 (C4¢),
24.0 (C7¢), 33.2 (NCH3), 35.0 (C6), 83.6 (C11), 101.7 (C7), 106.6
(N1¢-CHAHB), 110.1 (C3¢), 115.1 (13-CN), 117.1 (12-CN), 119.0
(C9¢), 121.8 (C5), 124.2 (C8¢), 125.3 (C2¢), 126.7 (C8-o-CPh), 127.9
(C4), 128.4 (C10-o-CPh), 128.9 (C8-m-CPh, C10-m-CPh, C8-p-CPh),
129.1 (C10-p-CPh), 130.0 (N1¢-CHX), 130.8 (C10-i-CPh), 131.7 (C8-
i-CPh), 144.8 (C2), 162.2 (C8), 168.6 (C10).
3
3JHB,HX = 15.7 Hz, JHA,HX = 8.8 Hz, 1 H, HX), 7.11 (s, 1 H, H4),
7.10–7.50 (m, 15 H, 3 Ph).
13C NMR (100.62 MHz, CDCl3): d = 33.1 (NCH3), 34.9 (C6), 83.6
(C11), 101.4 (C7), 110.2 (N1¢-CHAHB), 111.4 (C3¢), 112.8 (C4¢),
115.1 (13-CN), 117.0 (12-CN), 121.8 (C5), 126.5 (C8-o-CPh), 126.8
(C2¢), 127.8 (C4), 128.2 (C8-p-CPh), 128.3 (C10-o-CPh, C5¢-o-CPh),
128.7 (C5¢-m-CPh), 128.9 (C8-m-CPh, C10-m-CPh), 130.7 (C5¢),
130.8 (N1¢-CHX), 131.3 (C10-i-CPh), 131.6 (C8-i-CPh), 131.7 (C10-
p-CPh), 133.0 (C5¢-p-CPh), 135.2 (C5¢-i-CPh), 144.8 (C2), 162.4
(C8), 168.5 (C10).
Anal. Calcd for C33H29N5O: C, 77.47; H, 5.71; N, 13.69. Found: C,
77.95; H, 5.68; N, 13.22.
(Z)-3-{[(Z)-2-Cyano-1-phenylvinyl]oxy}-2-[(1-methyl-1H-imi-
dazol-2-yl)(1-vinyl-4,5-dihydro-1H-benzo[g]indol-2-yl)methyl]-
3-phenylprop-2-enenitrile (4e)
Following the typical procedure for 4a using acetylene 2 (0.254 g,
2 mmol), pyrrole-2-carbaldehyde 3e (0.223 g, 1 mmol), and 1-me-
thyl-1H-imidazole (1; 0.082 g, 1 mmol) in MeCN (2 mL) at 20–25
°C for 72 h gave 4e as a brown oil; yield: 0.141 g (43%). Initial pyr-
role-2-carbaldehyde 3e was recovered (0.092 g, conversion was
41%).
HRMS: m/z [M + H]+ calcd for C35H28N5O: 533.22; found: 533.10.
Anal. Calcd for C35H27N5O: C, 78.78; H, 5.10; N, 13.12. Found: C,
78.24; H, 4.98; N, 13.09.
(Z)-3-{[(Z)-2-Cyano-1-phenylvinyl]oxy}-2-[5-(4-methoxyphen-
yl)-1-vinyl-1H-pyrrol-2-yl](1-methyl-1H-imidazol-2-yl)meth-
yl]-3-phenyl-2-propenenitrile (4c)
IR (microlayer): 1028, 1077, 1113 (C–O–C), 1640 (C=C), 2219
cm–1 (CN).
Following the typical procedure for 4a using acetylene 2 (0.254 g,
2 mmol), pyrrole-2-carbaldehyde 3c (0.227 g, 1 mmol), and 1-meth-
yl-1H-imidazole (1, 0.082 g, 1 mmol) in MeCN (0.75 mL) at 20–25
°C for 26 h gave 4c as a dark orange oil; yield: 0.123 g (45%). Initial
pyrrole-2-carbaldehyde 3c was recovered (0.117 g, conversion was
49%).
1H NMR (400.13 MHz, CDCl3): d = 2.57 (m, 2 H, H4¢), 2.82 (m, 2
H, H5¢), 3.48 (s, 3 H, NCH3), 5.04 (s, 1 H, H11), 5.40 (d,
3
3JHB,HX = 15.7 Hz, 1 H, HB), 5.63 (d, JHA,HX = 8.8 Hz, 1 H, HA),
5.96 (s, 1 H, H6), 6.03 (s, 1 H, H3¢), 6.88 (s, 1 H, H5), 7.09 (s, 1 H,
H4), 7.00–7.40 (m, 15 H, H6¢, H7¢, H8¢, H9¢, HX, 2 Ph).
Synthesis 2011, No. 17, 2843–2847 © Thieme Stuttgart · New York