1970
M.Yu. Dvorko et al. / Tetrahedron 68 (2012) 1963e1971
¼14.2 Hz, 1H, CHa]), 8.51e8.53 (m, 1H, H-6, pyridine) ppm. 13
C
Phstyryl), 115.5 (d, 2J(C,F)¼22.3 Hz, C-2,0Phstyryl), 121.0 (C-
b
), 124.6 (d,
), 128.3
b
)
NMR (100.6 MHz, CDCl3) for Z-isomer:
d
¼22.0 (CH2-7), 23.1 (CH2-
4J(C,F)¼2.8 Hz, C-6, Phstyryl), 126.9 (Cp , Phpyrrole), 127.5 (C-
a
o
3
(C , Phpyrrole), 128.4 (Cm0, Phpyrrole), 129.9 (d, J(C,F)¼8.4 Hz, C-5,
0
6), 23.2 (CH2-4), 23.5 (CH2-5), 108.8 (C-3, pyrrole), 118.7 (C-b),
118.7 (C-9), 119.0 (C-2, pyrrole), 121.9 (C-5, pyridine), 123.7 (C-3,
pyridine), 126.7 (C- ), 128.0 (C-8), 136.0 (C-4, pyridine), 149.4 (C-
6, pyridine), 154.8 (C-2, pyridine); for E-isomer:
¼22.1 (CH2-7),
23.1 (CH2-6), 23.1 (CH2-4), 23.4 (CH2-5), 110.7 (C-3, pyrrole), 111.7
(C- ), 115.8 (C-2, pyrrole), 120.0 (C-9), 121.1 (C-5, pyridine), 121.5
(C-3, pyridine), 128.2 (C- ), 129.0 (C-8), 136.6 (C-4, pyridine),
149.4 (C-6, pyridine), 155.3 (C-2, pyridine) ppm. 15N NMR
(40.5 MHz, CDCl3) for Z-isomer:
¼ꢁ218.5 (pyrrole), ꢁ69.8 (pyr-
idine); for E-isomer:
Phstyryl), 132.8 (Ci0, Phpyrrole), 133.9 (C-2, pyrrole), 136.8 (d,
a
3J(C,F)¼8.2 Hz, C-1, Phstyryl), 162.8 (d, 1J(C,F)¼245.6 Hz, C-3, Phstyryl
)
d
ppm. 15N NMR (40.5 MHz, CDCl3) for Z-isomer:
Anal. Calcd for C18H14FN: C, 82.11; H, 5.36; F, 7.22; N, 5.32. Found:
C, 82.25; H, 5.48; F, 7.08; N, 5.21.
d
¼ꢁ219.1 ppm.
b
a
4.2.15. 2-Phenyl-1-[(Z/E)-2-(2-pyridinyl)ethenyl]-1H-pyrrole
(3n). Yield: 0.262 g (53%); yellow oil (mixture of E- and Z-iso-
mers), (Al2O3, eluentdhexane); Rf (25% Et2O/hexane) 0.48. IR
(film): 3079, 3060, 2929, 1650, 1602, 1585, 1563, 1496, 1465, 1434,
1415, 1328, 1307, 1286, 1240, 1172, 1150, 1078, 1051, 991, 980, 949,
915, 868, 841, 795, 786, 759, 741, 717, 699, 663, 639, 617, 607, 568,
d
d
¼ꢁ213.7 (pyrrole), ꢁ83.8 (pyridine) ppm.
Anal. Calcd for C15H16N2: C, 80.32; H, 7.19; N, 12.49. Found: C,
80.61; H, 7.24; N, 12.18.
4.2.13. 2-Phenyl-1-[(Z/E)-2-phenylethenyl]-1H-pyrrole (3l). Yield:
0.334 g (68%). Individual Z-isomer is yellow oil (Al2O3,
eluentdhexane); Rf (25% Et2O/hexane) 0.88; E-isomer is detected
by NMR. IR (film) for Z-isomer: 1649, 1602, 1494, 1467, 1416, 1316,
1176, 1167, 1076, 1029, 759, 717, 696, 606 cmꢁ1. 1H NMR (400.1 MHz,
514 cmꢁ1
.
1H NMR (400.1 MHz, CDCl3) for Z-isomer:
d
¼6.23 (dd,
3
3
3J(H-4,H-3)¼3.4 Hz, J(H-4,H-5)¼3.0 Hz, 1H, H-4), 6.38 (d, J(H-
a
,H-
¼9.3 Hz, 1H, CHb]), 6.39 (dd, 3J(H-3,H-4)¼3.4 Hz, 4J(H-3,H-5)¼1.6 Hz,
b
)
3
4
1H, H-3), 6.77 (dd, J(H-5,H-4)¼3.0 Hz, J(H-5,H-3)¼1.6 Hz, 1H, H-5),
3
6.85 (d, J(H-
¼9.3 Hz, 1H, CHa]), 7.11e7.18 (m, 2H, H-3, H-5,
a
,H-b)
3
3
p
m
0
CDCl3) for Z-isomer:
d
¼6.24 (dd, J(H-4,H-3)¼3.4 Hz, J(H-4,H-
pyridine), 7.26e7.30 (m, 1H, H , Ph), 7.35e7.38 (m, 2H, H 0, Ph),
¼2.7 Hz, 1H, H-4), 6.28 (d, 3J(H-
¼9.1 Hz, 1H, CHb]), 6.40 (dd,
7.45e7.49 (m, 2H, H , Ph), 7.54e7.58 (m, 1H, H-4, pyridine),
8.57e8.61 (m, 1H, H-6, pyridine); for E-isomer:
o
0
5)
a,H-b)
3J(H-3,H-4)¼3.4 Hz, J(H-3,H-5)¼1.7 Hz, 1H, H-3), 6.68 (d, J(H-
d
¼6.34 (dd, 3J(H-3,H-
4
3
a,H-
¼9.1 Hz, 1H, CHa]), 6.70 (dd, 3J(H-5,H-4)¼2.7 Hz, 4J(H-5,H-3)¼1.7 Hz,
¼3.5 Hz, J(H-3,H-5)¼1.6 Hz, 1H, H-3), 6.38 (dd, J(H-4,H-3)¼3.5 Hz,
4
3
b)
4)
1H, H-5), 7.22e7.27 (m, 3H, Ho, Hp, Phstyryl), 7.28e7.33 (m, 3H, Hm,
3J(H-4,H-5)¼3.0 Hz, 1H, H-4), 6.71 (d, J(H-
¼14.2 Hz, 1H, CHb]),
3
a
,H-b)
Phstyryl; H , Phpyrrole), 7.38e7.42 (m, 2H, Hm0, Phpyrrole), 7.51e7.55
7.07e7.11 (m, 1H, H-5, pyridine), 7.19e7.23 (m, 1H, H-3, pyridine),
p
0
o
0
3
3
4
(m, 2H, H , Phpyrrole); for E-isomer:
d
¼6.39 (dd, J(H-3,H-4)¼3.4 Hz,
7.28 (dd, J(H-5,H-4)¼3.0 Hz, J(H-5,H-3)¼1.6 Hz, 1H, H-5), 7.35e7.39
p o m
3
3
4J(H-3,H-5)¼1.7 Hz, 1H, H-3), 6.40 (dd, J(H-4,H-3)¼3.4 Hz, J(H-4,H-
(m, 1H, H , Ph), 7.44e7.46 (m, 4H, H , H 0, Ph), 7.59e7.63 (m, 1H,
0
0
¼3.4 Hz, 1H, H-4), 6.71 (d, 3J(H-
¼14.4 Hz, 1H, CHb]), 7.23 (dd,
H-4, pyridine), 7.94 (d, J(H-
¼14.2 Hz, 1H, CHa]), 8.47e8.51
3
5)
a
,H-b
)
a
,H-
b
)
3J(H-5,H-4)¼3.4 Hz, J(H-5,H-3)¼1.7 Hz, 1H, H-5), 7.24e7.26 (m, 1H, Hp,
(m, 1H, H-6, pyridine) ppm. 13C NMR (100.6 MHz, CDCl3) for Z-
4
Phstyryl), 7.33e7.40 (m, 4H, Ho, Hm, Phstyryl), 7.40 (d, J(H-
isomer:
d
¼109.8 (C-3, pyrrole), 109.9 (C-4, pyrrole), 121.9 (C-
b),
3
a
,H-
)
a
o
m
p
¼14.4 Hz, 1H, CH ]), 7.35e7.45 (m, 5H, H , H 0, H , Phpyrrole
122.1 (C-5, pyridine), 122.9 (C-5, pyrrole), 123.7 (C-3, pyridine),
0
0
b)
ppm. 13C NMR (100.6 MHz, CDCl3) for Z-isomer:
d
¼109.2 (C-3,
127.0 (C , Ph), 128.4 (C , Ph), 128.5 (C 0, Ph), 129.0 (C- ), 132.6 (Ci0,
a
p
o
m
0
0
pyrrole), 109.5 (C-4, pyrrole), 122.1 (C-
b
), 122.7 (C-5, pyrrole), 126.3
Ph), 134.1 (C-2, pyrrole), 136.1 (C-4, pyridine), 149.6 (C-6, pyridine),
154.1 (C-2, pyridine); for E-isomer:
¼110.9 (C-3, pyrrole), 111.2 (C-
4, pyrrole), 114.9 (C- ), 118.8 (C-5, pyrrole), 121.3 (C-3, pyridine),
121.5 (C-5, pyridine), 127.5 (C , Ph), 128.7 (C 0, Ph), 129.4 (C , Ph),
129.6 (C-
), 132.3 (Ci0, Ph), 135.3 (C-2, pyrrole), 136.6 (C-4, pyri-
dine), 149.5 (C-6, pyridine), 154.9 (C-2, pyridine) ppm. 15N NMR
(40.5 MHz, CDCl3) for Z-isomer:
¼ꢁ218.5 (pyrrole), ꢁ69.2 (pyri-
dine); for E-isomer:
p
0
o
0
(C-a
), 126.7 (C , Phpyrrole), 127.7 (Cp, Phstyryl), 128.2 (C , Phpyrrole),
d
128.3 (Cm, Phstyryl), 128.3 (Cm0, Phpyrrole), 128.7 (Co, Phstyryl), 132.8
b
(Ci0, Phpyrrole), 133.6 (C-2, pyrrole), 134.5 (Ci, Phstyryl); for E-isomer:
p
m
o
0
0
d
¼110.3 (C-3, pyrrole), 110.3 (C-4, pyrrole), 116.4 (C-
b
), 118.9 (C-5,
a
pyrrole), 125.9 (C-
a
), 126.0 (Co, Phstyryl), 126.8 (Cp, Phstyryl), 127.5
(C , Phpyrrole), 128.7 (Cm, Phstyryl), 128.7 (Cm0, Phpyrrole), 129.3 (C ,
d
p
0
o
0
Phpyrrole), 132.4 (Ci0, Phpyrrole),134.6 (C-2, pyrrole), 135.8 (Ci, Phstyryl
)
d
¼ꢁ211.2 (pyrrole), ꢁ81.9 (pyridine) ppm.
ppm. 15N NMR (40.5 MHz, CDCl3) for Z-isomer:
isomer:
5.71. Found: C, 88.27; H, 6.33; N, 5.49.
d
¼ꢁ218.5; for E-
Anal. Calcd for C17H14N2: C, 82.90; H, 5.73; N, 11.37. Found: C,
82.73; H, 5.54; N, 11.02.
d
¼ꢁ211.5 ppm. Anal. Calcd for C18H15N: C, 88.13; H, 6.16; N,
4.2.16. 1-[(Z/E)-2-Phenylethenyl]-2-(2-thienyl)-1H-pyrrole
(3o). Yield: 0.256 g (51%). Individual Z-isomer is pale yellow oil
(Al2O3, eluentdhexane); Rf (25% Et2O/hexane) 0.75; E-isomer was
detected by NMR. IR (film) for Z-isomer: 1648, 1574, 1505, 1494,
1465, 1448, 1432, 1409, 1346, 1299, 1204, 1162, 1073, 1029, 944, 843,
4.2.14. 2-Phenyl-1-[(Z/E)-2-(3-fluorophenyl)ethenyl]-1H-pyrrole
(3m). Yield: 0.321 g (61%). Individual Z-isomer is red oil (silica gel,
eluentdbenzene); Rf (25% Et2O/benzene) 0.89; E-isomer was
detected by 1H NMR. IR (film): 1651, 1610, 1582, 1494, 1486, 1467,
1441, 1415, 1320, 1251, 1178, 1131, 1077, 879, 787, 757, 717, 697, 693,
781, 693, 605, 559, 498 cmꢁ1
.
1H NMR (400.1 MHz, CDCl3) for Z-
3
3
663, 635, 522 cmꢁ1
.
1H NMR (400.1 MHz, CDCl3) for Z-isomer:
isomer:
6.32 (d, J(H-
d
¼6.15 (dd, J(H-4,H-3)¼3.4 Hz, J(H-4,H-5)¼2.9 Hz, 1H, H-4),
3
3
3
3
d
¼6.20 (d, J(H-
¼9.1 Hz, 1H, CHb]), 6.24 (dd, J(H-4,H-
¼9.1 Hz, 1H, CHb]), 6.41 (dd, J(H-3,H-4)¼3.4 Hz,
a
,H-
b
)
a,H-b)
3
3
3
4
¼3.4 Hz, J(H-4,H-5)¼2.9 Hz, 1H, H-4), 6.38 (dd, J(H-3,H-4)¼3.4 Hz,
4J(H-3,H-5)¼1.5 Hz, 1H, H-3), 6.59 (dd, J(H-5,H-4)¼2.9 Hz, J(H-5,H-
3)
3
4
3
4J(H-3,H-5)¼1.7 Hz, 1H, H-3), 6.67 (dd, J(H-5,H-4)¼2.9 Hz, J(H-5,H-
¼1.5 Hz, 1H, H-5), 6.74 (d, J(H-
¼9.1 Hz, 1H, CHa]), 7.01 (dd,
3)
a,H-b)
3
3
0
0
0
0
¼1.7 Hz, 1H, H-5), 6.71 (d, J(H-
¼9.1 Hz, 1H, CHa]),
J(H-4 ,H-5 )¼5.1 Hz, 3J(H-3 ,H-4 )¼3.7 Hz,1H, H-40, thiophene), 7.09 (dd,
3)
a,H-b)
3
4
0
0
0
0
6.85e6.87 (m, 1H, H-2, Phstyryl), 6.92e6.94 (m, 1H, H-4, Phstyryl),
J(H-3 ,H-4 )¼5.1 Hz,
J(H-3 ,H-5 )¼1.2 Hz, 1H, H-30, thiophene),
3
6.96e6.98 (m, 1H, H-6, Phstyryl), 7.20e7.24 (m, 1H, H-5, Phstyryl),
7.09e7.13 (m, 2H, Ho, Ph), 7.18e7.22 (m, 1H, Hp, Ph), 7.21 (dd, J(H-
p
4
7.26e7.30 (m, 1H, H , Phpyrrole), 7.34e7.38 (m, 2H, Hm0, Phpyrrole),
¼5.1 Hz, J(H-3 ,H-5 )¼1.2 Hz, 1H, H-50, thiophene), 7.21e7.25
0
0
0
0
0
4 ,H-5 )
¼6.35 (dd, 3J(H-3,H-
(m, 2H, Hm, Ph); for E-isomer:
d
¼6.30 (dd, 3J(H-4,H-3)¼3.4 Hz, 3J(H-4,H-
o
0
7.44e7.48 (m, 2H, H , Phpyrrole); for E-isomer:
d
4
3
3
4
¼3.3 Hz, J(H-3,H-5)¼1.6 Hz, 1H, H-3), 6.38 (dd, J(H-4,H-3)¼3.3 Hz,
¼2.8 Hz, 1H, H-4), 6.37 (dd, J(H-3,H-4)¼3.4 Hz, J(H-3,H-5)¼1.5 Hz,
4)
5)
3J(H-4,H-5)¼2.9 Hz, 1H, H-4), 6.64 (d, 3J(H-
¼14.7 Hz, 1H, CHb]),
1H, H-3), 6.65 (d, J(H-
a,H-b)
¼14.4 Hz, 1H, CHb]), 7.03 (dd, J(H-3 ,H-
3
3
0
a
,H-
b
)
4
3
0
0
0
6.80e6.90 (m, 3H, H-2, H-4, H-6, Phst4yryl), 7.17e7.21 (m, 1H, H-5,
¼3.7 Hz, J(H-3 ,H-5 )¼1.2 Hz, 1H, H-30, thiophene), 7.08 (dd, J(H-
4 )
3
3
0
0
0
0
Phstyryl), 7.23 (dd, J(H-5,H-4)¼2.9 Hz, J(H-5,H-3)¼1.6 Hz, 1H, H-5),
¼5.1 Hz, J(H-3 ,H-4 )¼3.7 Hz, 1H, H-40, thiophene), 7.19 (dd,
4 ,H-5 )
7.30e7.40 (m, 5H, H , Hm0
3J(H-5,H-4)¼2.8 Hz, J(H-5,H-3)¼1.5 Hz, 1H, H-5), 7.23e7.27 (m, 1H, Hp,
o
p
3
4
0
0
, H , Phpyrrole), 7.42 (d, J(H-
a,H-
3
4
¼14.7 Hz, 1H, CHa]) ppm. 13C NMR (100.6 MHz, CDCl3) for Z-
Ph), 7.31 (dd, J(H-4 ,H-5 )¼5.1 Hz, J(H-3 ,H-5 )¼1.2 Hz, 1H, H-50, thio-
0
0
0
0
b
)
2
3
isomer:
d
¼109.7 (C-3, pyrrole), 114.7 (d, J(C,F)¼21.3 Hz, C-4,
phene), 7.34e7.36 (m, 4H, Ho, Hm, Ph), 7.50 (d, J(H-
¼14.4 Hz,
a
,H-b)