LETTER
2.86–2.78 (m, 2 H), 2.60–2.45 (m, 1 H), 2.42–2.28 (m, 1 H),
Synthesis of Indolo- and Pyrrolobenzazepines
1007
Pyrrole 5c: 1H NMR (300 MHz, CDCl3): d = 7.46 (m, 1 H),
7.30 (m, 4 H), 7.14–7.02 (m, 2 H), 6.69 (dd, 1 H, J = 2.5, 1.8
Hz), 6.05 (dd, 1 H, J = 3.6, 2.6 Hz), 5.62 (dd, 1 H, J = 3.6,
1.6 Hz), 4.89 (s, 2 H), 2.83–2.70 (m, 2 H), 2.39 (m, 1 H),
2.28 (m, 1 H), 1.81 (m, 2 H). 13C NMR (75.5 MHz, CDCl3):
d = 141.0, 140.5, 135.7, 135.5, 132.4, 130.9, 130.5, 129.7,
129.5, 128.3, 127.9 (2), 127.6, 126.9, 125.5, 120.3, 108.9,
108.3, 52.4, 30.6, 30.5, 23.6. HRMS (EI): m/z calcd for
C22H18NCl [M+]: 331.1128; found: 331.1136.
1.94–1.80 (mc, 2 H). 13C NMR (75.5 MHz, CDCl3): d =
168.5, 156.7, 141.7, 140.5, 137.8, 136.1, 135.9, 135.6,
131.1, 130.6, 129.0, 128.6, 128.2, 127.8, 125.7, 123.8,
122.7, 121.4, 121.0, 111.5, 108.3, 102.3, 55.9, 51.9, 48.1,
31.4, 30.6, 23.8. HRMS (EI): m/z calcd for C29H26NO3 [M +
H+]: 436.1926; found: 436.1907.
Indole 3ae: 1H NMR (300 MHz, CDCl3): d = 8.06 (m, 2 H),
7.52 (m, 3 H), 7.42 (d, 1 H, J = 7.9 Hz), 7.28–7.15 (m, 4 H),
7.00 (m, 1 H), 5.85 (s, 1 H), 5.17 (s, 2 H), 4.38 (q, 2 H,
J = 7.1 Hz), 2.86 (t, 2 H, J = 6.5 Hz), 2.45 (t, 2 H, J = 6.3
Hz), 1.90 (m, 2 H), 1.39 (t, 3 H, J = 7.1 Hz). 13C NMR (75.5
MHz, CDCl3): d = 166.8, 142.8, 140.2 (2), 136.3, 135.8,
135.7, 134.9, 134.1, 131.5, 131.2, 130.8, 128.8, 128.4,
128.5, 128.3, 128.2, 125.7, 121.9, 120.9, 119.8, 108.8,102.6,
61.3, 47.9, 31.7, 30.3, 24.3, 14.6. HRMS (EI): m/z calcd for
C29H25NO2 [M+]: 419.1885; found: 419.1882.
Pyrrole 5d: 1H NMR (300 MHz, CDCl3): d = 7.34–7.29 (m,
1 H), 7.20–7.08 (m, 4 H), 7.02–6.95 (m, 2 H), 6.66 (dd, 1 H,
J = 2.4, 1.8 Hz), 6.03 (dd, 1 H, J = 3.6, 2.6 Hz), 5.64 (dd, 1
H, J = 3.6, 1.7 Hz), 4.97 (d, 1 H, J = 13.5 Hz), 4.90 (d, 1 H,
J = 13.4 Hz) 3.75 (s, 3 H), 2.80–2.76 (m, 2 H), 2.42–2.28 (m,
2 H), 1.85–1.79 (m, 2 H). 13C NMR (75.5 MHz, CDCl3): d =
157.4, 138.9, 134.5, 130.6, 129.6, 129.5, 127.2, 126.9,
126.2, 124.3, 123.8, 119.6, 118.8, 117.6, 110.1 (2), 107.6,
107.0, 54.6, 51.4, 29.8, 29.6, 22.7. HRMS (EI): m/z calcd for
C23H21NO [M+]: 327.1627; found: 327.1623.
Indole 3af: 1H NMR (300 MHz, CDCl3): d = 7.95 (d, 1 H,
J = 8.3 Hz), 7.90 (m, 2 H), 7.60–7.30 (m, 8 H), 7.16 (m, 2 H),
6.96 (m, 1 H), 5.84 (s, 1 H), 5.30 (s, 2 H), 2.82 (t, 2 H, J = 6.4
Hz), 2.47 (m, 1 H), 2.24 (m, 1 H), 1.78 (m, 2 H). 13C NMR
(75.5 MHz, CDCl3): d = 140.6, 140.0, 135.9, 135.7 (2),
134.2, 131.8, 130.4, 128.6 (2), 128.5, 128.3 (2), 128.2,
127.7, 126.8, 126.5, 126.1, 126.0(2), 125.8, 121.7, 120.9,
119.6, 108.7, 102.0, 48.2, 31.5, 30.6, 24.0. HRMS (EI):
m/z calcd for C30H23N [M+]: 397.1813; found: 397.1843.
Indole 3ag: 1H NMR (300 MHz, CDCl3): d = 8.10–8.05 (m,
1 H), 7.82–7.77 (m, 2 H), 7.60 (s, 1 H), 7.51 (br d, 1 H,
J = 8.2 Hz), 7.38–7.11 (m, 10 H), 6.99 (mc, 1 H), 5.79 (s,
1 H), 5.20 (s, 2 H), 2.84 (t, 2 H, J = 6.5 Hz), 2.52–2.42
(m, 2 H), 2.37 (s, 3 H), 1.96 (mc, 2 H). 13C NMR (75.5 MHz,
CDCl3): d = 145.2, 140.4, 137.8, 136.1, 135.9, 135.7, 135.5,
135.4, 131.2, 130.1, 128.6, 128.4, 128.2, 127.0, 125.7,
125.2, 124.6, 123.9, 121.9, 121.8, 120.8, 120.6, 119.7,
114.3, 108.8, 101.6, 139.5, 124.4, 48.0, 31.6, 30.4, 24.3,
21.9. HRMS (EI): m/z calcd for C35H29N2O2S [M + H+]:
541.1921; found: 541.1944.
Pyrrole 5e: 1H NMR (300 MHz, CDCl3): d = 8.04–8.00 (m,
1 H), 7.99–7.97 (m, 1 H), 7.50–7.48 (m, 2 H), 7.22–7.19 (m,
1 H), 7.15–7.10 (m, 2 H), 6.72 (dd, 1 H, J = 1.8, 2.5 Hz), 6.04
(dd, 1 H, J = 2.5, 3.7 Hz), 5.54 (dd, 1 H, J = 1.8, 3.7 Hz),
4.94 (s, 2 H), 4.38 (q, 2 H, J = 7.1 Hz), 2.84 (t, 2 H, J = 6.4
Hz), 2.37 (m, 2 H), 1.86 (quint, 2 H, J = 6.4 Hz), 1.39 (t, 3
H, J = 7.1 Hz). 13C NMR (75.5 MHz, CDCl3): d = 166.8,
143.0, 139.9, 136.3, 135.4, 133.9, 133.8, 131.6, 130.9, 130.7
(2), 128.6, 128.4, 128.1, 127.7, 125.5, 120.7, 110.1, 108.4,
61.2, 52.7, 31.2, 30.4, 24.3, 14.5. HRMS (EI): m/z calcd for
C25H23NO2 [M+]: 369.1729; found: 369.1721.
Pyrrole 5f: 1H NMR (300 MHz, CDCl3): d = 7.92 (d, 1 H,
8.3 Hz), 7.86 (m, 2 H), 7.53 (m, 1 H), 7.46 (m, 1 H), 7.40 (m,
2 H), 7.23 (d, 1 H, J = 9.2 Hz), 7.20 (m, 1 H), 7.14 (m, 1 H),
6.71 (dd, 1 H, J = 2.5, 1.8 Hz), 5.97 (dd, 1 H, J = 3.7, 2.6
Hz), 5.51 (br s, 1 H), 5.06 (s, 2 H), 2.78 (t, 2 H, J = 6.2 Hz),
2.38 (m, 1 H), 2.17 (m, 1 H), 1.73 (m, 2 H). 13C NMR (75.5
MHz, CDCl3): d = 140.3 (2), 136.4, 135.5, 134.1, 133.8,
131.7, 128.5 (2), 128.3, 127.7, 127.3, 126.3, 126.1, 126.0(2),
125.7, 120.7, 120.6, 109.7, 108.5, 53.0, 31.0, 30.8, 24.0.
HRMS (EI): m/z calcd for C26H21N [M+]: 347.1674; found:
347.1667.
Indole 3bg: 1H NMR (300 MHz, CDCl3): d = 8.12–8.07 (m,
2 H), 7.89 (dd, 1 H, J = 8.7, 1.6 Hz), 7.81–7.76 (m, 2 H), 7.60
(s, 1 H), 7.50 (br d, 1 H, J = 8.9 Hz), 7.39–7.14 (m, 8 H), 5.80
(s, 1 H), 5.21 (s, 2 H), 3.88 (s, 3 H), 2.86 (t, 2 H, J = 6.5 Hz),
2.55–2.45 (m, 2 H), 2.41 (s, 3 H), 1.96 (m, 2 H). 13C NMR
(75.5 MHz, CDCl3): d = 168.3, 145.4, 140.6, 138.8, 137.9,
135.9, 135.6, 135.4, 135.4, 131.0, 130.2, 128.9, 128.7,
127.6, 127.0, 125.8, 125.3, 124.7, 124.2, 124.0, 123.8,
123.1, 121.7, 121.5, 120.4, 114.4, 108.5, 102.9, 52.0, 48.3,
31.7, 30.4, 24.2, 21.8. HRMS (EI): m/z calcd for
Pyrrole 5g: 1H NMR (400 MHz, CDCl3): d = 7.23–7.16 (m,
5 H), 7.14–7.10 (m, 2 H), 6.70–6.69 (m, 1 H), 6.05 (dd, 1 H,
J = 3.7, 2.6 Hz), 5.60 (dd, 1 H, J = 3.7, 1.7 Hz), 4.93 (s, 2 H),
2.85 (t, 2 H, J = 6.5 Hz), 2.43–2.39 (m, 2 H), 2.41 (s, 3 H),
1.87 (quint, 2 H, J = 6.4 Hz). 13C NMR (75.5 MHz, CDCl3):
d = 139.9, 139.8, 136.7, 136.3, 135.3, 132.6, 130.2, 129.3,
129.1, 128.9, 128.3, 127.4, 125.3, 120.4, 109.9, 108.3, 52.7,
31.1, 30.5, 24.5, 21.4. HRMS (EI): m/z calcd for C23H21N
[M+]: 311.1674; found: 311.1668.
C37H31ON2O4S [M + H+]: 599.1968; found: 599.1999.
Pyrrole 5a: 1H NMR (300 MHz, CDCl3): d = 7.40 (m, 1 H),
7.30 (m, 4 H), 7.18 (d, 1 H, J = 7.3 Hz), 7.12 (m, 2 H), 6.70
(m, 1 H, J = 2.5 Hz), 6.04 (dd, 1 H, J = 3.7, 2.6 Hz), 5.58 (dd,
1 H, J = 3.7, 1.8 Hz), 4.93 (s, 2 H), 2.84 (t, 2 H, J = 6.5 Hz),
2.40 (br s, 2 H), 1.90–1.82 (m, 2 H). 13C NMR (75.5 MHz,
CDCl3): d = 142.9, 139.9, 136.7, 135.4, 132.7, 130.3, 129.5,
128.5 (2), 128.2, 127.6, 126.9, 125.5, 120.5, 110.1, 108.4,
52.8, 31.2, 30.6, 24.5. HRMS (EI): m/z calcd for C22H19N
[M+]: 297.1517; found: 297.1522.
Pyrrole 5h: 1H NMR (300 MHz, CDCl3): d = 7.23–7.18 (m,
1 H), 7.13–7.08 (m, 2 H), 6.72 (dd, 1 H, J = 2.3, 2.0 Hz), 6.51
(s, 2 H), 6.08 (dd, 1 H, J = 3.7, 2.6 Hz), 5.73 (dd, 1 H,
J = 3.7, 1.7 Hz), 4.93 (s, 2 H), 3.91 (s, 3 H), 3.86 (s, 6 H),
2.86 (t, 2 H, J = 6.5 Hz), 2.48–2.40 (m, 2 H), 1.89 (quint, 2
H, J = 6.4 Hz). 13C NMR (100 MHz, CDCl3): d = 153.3,
139.7, 138.3, 136.8, 136.5, 135.3, 133.8, 132.4, 130.4,
128.4, 127.6, 125.4, 120.6, 109.8, 108.3, 106.4, 61.1, 56.3,
52.7, 31.1, 30.4, 24.5. ESI-HRMS: m/z calcd for C25H26NO3
[M + H+]: 388.1894; found: 388.1907.
Pyrrole 5b: 1H NMR (400 MHz, CDCl3): d = 8.29 (d, 2 H,
J = 8.8 Hz), 7.48 (d, 2 H, J = 8.8 Hz), 7.24–7.22 (m, 1 H),
7.16–7.13 (m, 2 H), 6.74 (dd, 1 H, J = 2.5, 1.8 Hz), 6.07 (dd,
1 H, J = 3.7, 2.6 Hz), 5.52 (dd, 1 H, J = 3.7, 1.7 Hz), 4.96 (s,
2 H), 2.87 (t, 2 H, J = 6.5 Hz), 2.37 (t, 2 H, J = 6.5 Hz), 1.88
(quint, 2 H, J = 6.5 Hz). 13C NMR (75.5 MHz, CDCl3): d =
149.7, 147.0, 139.9, 135.9, 135.3, 132.8, 131.1, 130.6, 130.4,
128.6, 128.1, 125.6, 123.9, 121.1, 110.2, 108.6, 52.7, 31.2,
30.3, 24.3. HRMS (EI): m/z calcd for C22H18N2O2 [M+]:
342.1368; found: 342.1383.
Compound 7b: 1H NMR (400 MHz, CDCl3): d = 8.12–8.09
(m, 2 H), 7.77–7.74 (m, 1 H), 7.23–7.19 (m, 1 H), 7.13–7.08
(m, 2 H), 6.49 (t, 2 H, J = 2.1 Hz), 6.08 (t, 2 H, J = 2.1 Hz),
5.32 (d, 1 H, J = 14.6 Hz), 5.01 (d, 1 H, J = 14.6 Hz), 3.31–
3.23 (m, 1 H), 3.09 (d, 1 H, J = 7.7 Hz), 2.92 (d, 1 H, J = 7.8
Hz), 2.64 (dt, 1 H, J = 13.8, 3.1 Hz), 2.57–2.51 (m, 1 H),
2.35 (d, 1 H, J = 4.2 Hz), 2.30 (dt, 1 H, J = 4.3, 13.5 Hz),
Synlett 2009, No. 6, 1004–1008 © Thieme Stuttgart · New York