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1 mmol) and 4-cyanobenzenesulfonyl chloride (504 mg, 2.5 mmol),
the residue was purified by flash chromatography on silica gel
(pentane–Et2O, 85:15) to afford the desired compound 23 (333 mg,
(q, J=3.7 Hz), 110.5, 108.4, 48.0 ppm; elemental analysis: calcd (%)
for C25H15F6N (443.38): C 67.72, H 3.41; found: C 67.51, H 3.59.
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1-(2-Bromobenzyl)-2,5-bis(3,5-dichlorophenyl)pyrrole (29): After
following procedure B with 1-(2-bromobenzyl)pyrrole (118 mg,
0.5 mmol) and 3,5-dichlorobenzenesulfonyl chloride (306 mg,
1.25 mmol), the residue was filtrated on a silica plug and directly
used in the next reaction.
76%). H NMR (400 MHz, CDCl3): d=7.62 (d, J=8.3 Hz, 4H), 7.47–
7.41 (m, 5H), 7.19 (t, J=7.4 Hz, 1H), 7.09 (t, J=7.7 Hz, 1H), 6.55 (s,
2H), 6.42 (d, J=7.7 Hz, 1H), 5.27 ppm (s, 2H); 13C NMR (100 MHz,
CDCl3): d=137.3, 137.1, 136.4, 132.8, 132.4, 129.2, 128.8, 128.0,
127.1, 121.0, 118.7, 112.3, 110.9, 49.6 ppm; elemental analysis: calcd
(%) for C25H16BrN3 (438.32): C 68.50, H 3.68; found: C 68.64, H 3.89.
1,3-Dichloro-7-(3,5-dichlorophenyl)dibenzo[c,e]pyrrolo[1,2-a]aze-
pine (30): After following procedure C with the crude mixture of 1-
(2-bromobenzyl)-2,5-bis(3,5-dichlorophenyl)pyrrole (29; 158 mg,
0.3 mmol), the residue was purified by flash chromatography on
silica gel (pentane–Et2O, 85:15) to afford the desired compound 30
(122 mg, 91%). 1H NMR (400 MHz, CDCl3): d=7.76 (dd, J=2.6,
6.9 Hz, 1H), 7.57 (d, J=2.2 Hz, 1H), 7.53 (d, J=2.2 Hz, 1H), 7.44–
7.38 (m, 3H), 7.34 (d, J=2.0 Hz, 2H), 7.30–7.27 (m, 2H), 6.50 (d, J=
3.8 Hz, 1H), 6.26 (d, J=3.8 Hz, 1H), 4.98 (d, J=13.9 Hz, 1H),
4.69 ppm (d, J=14.1 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=138.0,
135.6, 135.6, 135.1, 134.8, 134.3, 133.7, 133.3, 132.8, 132.7, 132.5,
128.8, 128.8, 128.1, 127.5, 127.3, 127.1, 127.0, 110.5, 108.8,
47.7 ppm; elemental analysis: calcd (%) for C23H13Cl4N (445.16): C
62.06, H 2.94; found: C 62.01, H 3.07.
7-(4-Cyanophenyl)dibenzo[c,e]pyrrolo[1,2-a]azepine-2-carboni-
trile (24): After following procedure C with 4,4’-(1-(2-bromobenzyl)-
pyrrole-2,5-diyl)dibenzonitrile (23; 219 mg, 0.5 mmol), the residue
was purified by flash chromatography on silica gel (pentane–Et2O,
1
85:15) to afford the desired compound 24 (111 mg, 62%). H NMR
(400 MHz, CDCl3): d=7.93 (s, 1H), 7.79 (t, J=8.9 Hz, 3H), 7.70 (d,
J=8.2 Hz, 1H), 7.63 (d, J=7.3 Hz, 1H), 7.57 (d, J=8.3 Hz, 2H), 7.50
(quint., J=6.5 Hz, 2H), 7.34 (d, J=7.5 Hz, 1H), 6.62 (d, J=3.9 Hz,
1H), 6.39 (d, J=3.9 Hz, 1H), 5.02 (d, J=14.2 Hz, 1H), 4.72 ppm (d,
J=14.3 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=146.4, 138.3, 137.1,
137.0, 136.8, 135.7, 134.9, 134.4, 132.5, 131.0, 130.4, 129.9, 129.4,
129.2, 129.1, 128.0, 127.5, 118.8, 111.7, 110.9, 110.6, 110.0,
48.2 ppm; elemental analysis: calcd (%) for C25H15N3 (357.41): C
84.01, H 4.23; found: C 83.86, H 4.38.
1-(2-Bromobenzyl)-2,5-bis(2,3,4-trifluorophenyl)pyrrole
(31):
After following procedure B with 1-(2-bromobenzyl)pyrrole
(236 mg, 1 mmol) and 2,3,4-trifluorobenzenesulfonyl chloride
(288 mg, 1.25 mmol), the residue was filtrated on a silica plug and
directly used in the next reaction.
1-(2-Bromobenzyl)-2,5-bis(4-(trifluoromethyl)phenyl)pyrrole (25):
After following procedure B with 1-(2-bromobenzyl)pyrrole
(118 mg, 0.5 mmol) and 4-(trifluoromethyl)benzenesulfonyl chloride
(306 mg, 1.25 mmol), the residue was filtrated on a silica plug and
directly used in the next reaction.
2,3,4-Trifluoro-7-(2,3,4-trifluorophenyl)dibenzo[c,e]pyrrolo[1,2-
a]azepine (32): After following procedure C with the crude mixture
of 1-(2-bromobenzyl)-2,5-bis(2,3,4-trifluorophenyl)pyrrole (31), the
residue was purified by flash chromatography on silica gel (pen-
tane–Et2O, 85:15) to afford the desired compound 32 (270 mg,
65%). 1H NMR (400 MHz, CDCl3): d=7.49 (d, J=7.5 Hz, 1H), 7.41
(dt, J=1.6, 7.5 Hz, 1H), 7.34 (dt, J=1.6, 7.1 Hz, 1H), 7.26–7.21 (m,
1H), 7.12–7.06 (m, 3H), 6.63 (dd, J=3.8, 4.8 Hz, 1H), 6.31 (d, J=
3.8 Hz, 1H), 4.75 ppm (s, 2H); 13C NMR (100 MHz, CDCl3): d=142.9
(dm, J=246.3 Hz), 141.8 (dm, J=246.3 Hz), 140.4 (dm, J=
246.3 Hz), 139.8 (dm, J=246.3 Hz), 137.7, 137.1, 133.2 (m), 130.0,
128.9 (d, J=6.7 Hz), 127.7, 126.5 (dm, J=237.2 Hz), 125.9 (t, J=
5.9 Hz), 125.8, 124.4, 123.7 (dm, J=246.3 Hz), 122.4, 118.4 (d, J=
13.3 Hz), 118.3 (d, J=13.3 Hz), 113.2 (dd, J=3.5 and 18.6 Hz), 112.2
(dd, J=4.2, 18.6 Hz), 111.7 (d, J=7.6 Hz),111.3, 48.3 ppm; elemental
analysis: calcd (%) for C23H11F6N (415.34): C 66.51, H 2.67; found: C
66.89, H 2.94.
2-(Trifluoromethyl)-7-(4-(trifluoromethyl)phenyl)dibenzo[c,e]pyr-
rolo[1,2-a]azepine (26): After following procedure C with the
crude mixture of 1-(2-bromobenzyl)-2,5-bis(4-(trifluoromethyl)phe-
nyl)pyrrole (25), the residue was purified by flash chromatography
on silica gel (pentane–Et2O, 85:15) to afford the desired compound
26 (171 mg, 77%). 1H NMR (300 MHz, CDCl3): d=7.81 (brs, 1H),
7.75–7.66 (m, 3H), 7.62–7.57 (m, 2H), 7.51 (d, J=8.1 Hz, 2H), 7.40
(qq, J=6.7, 7.4 Hz, 2H), 7.26 (dd, J=1.9, 7.2 Hz, 1H), 6.51 (d, J=
3.8 Hz, 1H), 6.27 (d, J=3.8 Hz, 1H), 4.96 (d, J=14.2 Hz, 1H),
4.64 ppm (d, J=14.1 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=139.1,
137.4, 136.4, 135.1, 134.5, 134.4, 130.3, 129.7, 129.6, 129.4 (q, J=
30.1 Hz), 129.3, 129.0 (q, J=29.5 Hz), 128.9, 128.7, 125.6, 125.5 (q,
J=270.3 Hz), 124.6 (m), 124.2 (q, J=271.3 Hz), 110.8, 109.0,
48.1 ppm; elemental analysis: calcd (%) for C25H15F6N (443.38): C
67.72, H 3.41; found: C 67.99, H 3.18.
1-(2-Bromobenzyl)-2,5-bis(3-(trifluoromethyl)phenyl)pyrrole (27):
After following procedure B with 1-(2-bromobenzyl)pyrrole
(118 mg, 0.5 mmol) and 3-(trifluoromethyl)benzenesulfonyl chloride
(306 mg, 1.25 mmol), the residue was filtrated on a silica plug and
directly used in the next reaction.
Methyl
3-(1-(2-bromobenzyl)-5-(4-isocyanophenyl)pyrrol-2-yl)-
thiophene-2-carboxylate (33): After following procedure A with 1-
(2-bromobenzyl)-2-(4-cyanophenyl)pyrrole (337 mg, 1 mmol) and 4-
cyanobenzenesulfonyl chloride (300 mg, 1.25 mmol), the residue
was purified by flash chromatography on silica gel (pentane-Et2O,
3-(Trifluoromethyl)-7-(3-(trifluoromethyl)phenyl)dibenzo[c,e]pyr-
rolo[1,2-a]azepine (28): After following procedure C with the
crude mixture of 1-(2-bromobenzyl)-2,5-bis(3-(trifluoromethyl)phe-
nyl)pyrrole (27), the residue was purified by flash chromatography
on silica gel (pentane–Et2O, 85:15) to afford the desired compound
1
65-35) to afford the desired compound 33 (220 mg, 46%). H NMR
(400 MHz, CDCl3): d=7.58 (d, J=8.0 Hz, 2H), 7.44 (d, J=8.0 Hz,
2H), 7.38 (d, J=5.1 Hz, 1H), 7.33 (d, J=8.0 Hz, 1H), 7.09 (t, J=
7.6 Hz, 1H), 6.97 (dd, J=7.2, 8.0 Hz, 1H), 6.85 (d, J=5.1 Hz, 1H), 6.5
(d, J=3.7 Hz, 1H), 6.41 (d, J=8.6 Hz, 1H), 6.38 (d, J=3.7 Hz, 1H),
1
28 (109 mg, 49%). H NMR (400 MHz, CDCl3): d=7.94 (s, 1H), 7.77–
1
5.15 (s, 2H), 3.83 ppm (s, 3H); H NMR (400 MHz, CDCl3): d=161.9,
7.73 (m, 2H), 7.69–7.64 (m, 4H), 7.63 (s, 1H), 7.52–7.45 (m, 2H),
7.39–7.34 (m, 1H), 6.59 (d, J=3.8 Hz, 1H), 6.35 (d, J=3.8 Hz, 1H),
4.99 (d, J=14.3 Hz, 1H), 4.71 ppm (d, J=14.2 Hz, 1H); 13C NMR
(100 MHz, CDCl3): d=139.2, 139.0, 137.6, 134.3, 134.0, 133.6, 132.5,
131.1 (q, J=30.6 Hz), 131.0, 130.5, 130.31 (q, J=30.6 Hz), 129.2,
128.9, 128.8, 127.5, 126,2 (q, J=3.7 Hz), 125.9 (q, J=3.7 Hz), 124.2
(q, J=272.0 Hz), 124.1 (q, J=272.0 Hz), 124.0 (q, J=3.7 Hz), 123.4
138.5, 137.7, 137.6, 134.5, 132.4, 132.3, 131.8, 131.0, 130.5, 129.4,
128.6, 127.6, 121.2, 119.0, 111.6, 111.3, 110.2, 52.2, 49.3 ppm; ele-
mental analysis: calcd (%) for C24H17BrN2O2S (477.38): C 60.39, H
3.59; found: C 60.76, H 3.85.
4-(Benzo[e]pyrrolo[1,2-a]thieno[3,4-c]azepin-6-yl)benzonitrile
(34): After following procedure C with methyl 3-(1-(2-bromoben-
ChemCatChem 2015, 7, 3544 – 3554
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