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form-d): d=7.93 (d, J=8.8 Hz, 1H), 7.91 (s, 1H), 7.74–7.72 (m, 1H),
7.58–7.54 (m, 1H), 7.46–7.42 (m, 1H), 7.23–7.21 (m, 2H), 7.17–7.13
(m, 1H), 6.98–6.96 (m, 2H), 4.56 (t, J=5.6 Hz, 1H), 3.13–3.06 (m,
1H), 3.05–2.97 (m, 1H), 2.35–2.27 (m, 1H), 2.18–2.11 (m, 1H), 1.92–
1.86 (m, 1H), 1.81–1.75 ppm (m, 1H); 13C NMR (100 MHz, Chloro-
form-d): d=160.2, 146.9, 146.2, 135.2, 131.4, 128.8, 128.7, 128.4,
128.1, 127.3, 126.7, 125.8, 125.7, 48.2, 32.5, 29.2, 19.0 ppm; IR (ATR):
3058, 3027, 2932, 2858, 1598, 1559, 1491, 1446, 1416, 1378, 1341,
for 4 h. Upon completion of the reaction, the reaction system was
cooled to room temperature. The solvent was removed under
vacuum and the residue was purified by column chromatography
on silica gel (petroleum ether/EtOAc, 9:1) to give compound 10a
(23 mg, 62%) as a pale yellow solid. M.p. 145–1478C; 1H NMR
(400 MHz, Chloroform-d): d=7.95–7.93 (m, 1H), 7.63 (s, 1H), 7.60
(d, J=8.4 Hz, 1H), 7.54–7.52 (m, 1H), 7.43–7.37 (m, 2H), 7.32–7.29
(m, 2H), 7.19–7.15 (m, 1H), 6.92–6.91 (m, 1H), 3.96 (t, J=7.8 Hz,
2H), 3.30–3.26 (m, 2H), 1.45–1.40 (m, 2H), 1.14–1.10 ppm (m, 2H);
13C NMR (100 MHz, Chloroform-d): d=161.0, 147.7, 138.9, 135.8,
130.2, 128.3, 127.8, 127.1, 127.0, 126.94, 126.92, 126.5, 126.0, 125.6,
124.3, 122.1, 114.3, 52.4, 25.7, 4.1, 0.7 ppm; IR (ATR): 3053, 2924,
2856, 1641, 1573, 1490, 1430, 1364, 1316, 1235, 1146, 1111, 1046,
974, 940, 904, 860, 804, 756 cmÀ1; HRMS (EI) m/z calcd for C21H18N2
[M+]: 298.1470; found: 298.1461.
1306, 1267, 1151, 1077, 1029, 955, 917, 857, 752, 701, 617 cmÀ1
;
HRMS (EI) m/z calcd for C19H17N [M+]: 259.1361; found: 259.1360.
Procedure for the synthesis of 3-(cyclopent-1-en-1-yl)-2-(9H-
fluoren-9-yl)-1H-indole (7)
To an oven-dried Schlenk tube that was equipped with a magnetic
stirrer bar were sequentially added 6 (0.25 mmol), 2 f (0.3 mmol,
1.2 equiv), and xylene (1 mL) under a nitrogen atmosphere. Then,
a condenser was fitted and the mixture was heated at reflux for
6 h. Upon completion of the reaction, the reaction system was
cooled to room temperature. The solvent was removed under
vacuum and the residue was purified by column chromatography
on silica gel (petroleum ether/EtOAc, 50:1) to give compound 7
Typical procedure for the synthesis of 1-phenyl-1H-pyrro-
lo[2,3-b]-quinoline (11a)
To an oven-dried Schlenk tube that was equipped with a magnetic
stirrer bar were sequentially added 9a (0.15 mmol), DDQ
(0.15 mmol), and toluene (1 mL) under a nitrogen atmosphere.
Then, a condenser was fitted and the mixture was stirred at 508C
for 8 h. Upon completion of the reaction, the reaction system was
cooled to room temperature, and NaHSO3 (aqueous) was added to
quench the reaction. The mixture was extracted with EtOAc. The
combined extracts were dried over Na2SO4 and concentrated in
vacuo. The residue was purified by column chromatography on
silica gel (petroleum ether/EtOAc, 50:1) to give compound 11 a
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(45 mg, 52%) as a yellow solid. M.p. 191–1938C; H NMR (400 MHz,
Chloroform-d): d=7.96 (br, 1H), 7.88–7.86 (m, 2H), 7.40–7.36 (m,
2H), 7.32–7.30 (m, 2H), 7.22–7.18 (m, 3H), 6.97–6.93 (m, 1H), 6.57–
6.53 (m, 1H), 6.37–6.35 (m, 1H), 6.05 (d, J=8.0 Hz, 1H), 5.63 (s,
1H), 3.05–2.99 (m, 2H), 2.66–2.60 (m, 2H), 2.13 ppm (quintet, J=
7.6 Hz, 2H); 13C NMR (100 MHz, Chloroform-d): d=147.8, 140.8,
135.7, 134.8, 133.7, 128.5, 127.1, 127.0, 125.1, 122.0, 120.0, 119.8,
119.1, 111.4, 110.2, 45.9, 35.0, 33.2, 23.5 ppm; IR (ATR): 3439, 3047,
2843, 2361, 1701, 1442, 1298, 1264, 1152, 1009, 795, 732, 701, 666,
617 cmÀ1; HRMS (EI) m/z calcd for C26H21N [M+]: 347.1674; found:
347.1671.
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(21 mg, 57%) as a pale yellow oil. H NMR (400 MHz, Chloroform-
d): d=8.41 (s, 1H), 8.11 (d, J=8.8 Hz, 1H), 7.97–7.93 (m, 3H), 7.73
(d, J=3.6 Hz, 1H), 7.66–7.62 (m, 1H), 7.57–7.53 (m, 2H), 7.45–7.41
(m, 1H), 7.36–7.32 (m, 1H), 6.75 ppm (d, J=4.0 Hz, 1H); 13C NMR
(100 MHz, Chloroform-d): d=148.8, 145.2, 138.6, 131.6, 129.3,
128.5, 128.0, 127.84, 127.76, 125.9, 124.9, 123.4, 122.9, 101.4 ppm;
IR (ATR): 3054, 2924, 2854, 1738, 1597, 1531, 1500, 1422, 1393,
1341, 1294, 1238, 1206, 1147, 1020, 953, 903, 847, 783, 753, 694,
669 cmÀ1; HRMS (EI) m/z calcd for C17H12N2 [M+]: 244.1000; found:
244.0999.
Typical procedure for the synthesis of 1-phenyl-2,3-dihydro-
1H-pyrrolo[2,3-b]quinoline (9a)
To an oven-dried Schlenk tube that was equipped with a magnetic
stirrer bar were sequentially added 1a (0.25 mmol), 8a (0.5 mmol),
and toluene (1 mL) under a nitrogen atmosphere. Then, a condens-
er was fitted and the mixture was stirred at 658C for 4 h. Upon
completion of the reaction, the reaction system was cooled to
room temperature. The solvent was removed under vacuum and
the residue was purified by column chromatography on silica gel
(petroleum ether/EtOAc, 20:1) to give compound 9a (48 mg, 78%)
Procedure for the synthesis of (2,3-dihydro-1H-pyrrolo[2,3-
b]quinolin-1-yl)(phenyl)methanone (12)
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as a pale yellow solid. M.p. 180–1828C; H NMR (500 MHz, Chloro-
To a stirred solution of 9h (0.15 mmol) and triethyl benzyl ammoni-
um chloride (TEBAC) (0.45 mmol) in dichloromethane (3 mL) was
added finely ground KMnO4 (0.45 mmol), and the solution was
stirred at reflux for 8 h. Upon completion of the reaction, the reac-
tion system was cooled to room temperature, and NaHSO3 (aque-
ous) was added to quench the reaction. The mixture was extracted
with dichloromethane. The combined extracts were dried over
Na2SO4 and concentrated in vacuo. The residue was purified by
column chromatography on silica gel (petroleum ether/EtOAc, 7:1)
form-d): d=8.05 (d, J=8.0 Hz, 2H), 7.80 (d, J=8.5 Hz, 1H), 7.60 (s,
1H), 7.53 (d, J=7.5 Hz, 1H), 7.51–7.48 (m, 1H), 7.43–7.40 (m, 2H),
7.25–7.22 (m, 1H), 7.06 (t, J=7.3 Hz, 1H), 4.09 (t, J=8.0 Hz, 2H),
3.24–3.21 ppm (m, 2H); 13C NMR (125 MHz, Chloroform-d): d=
158.5, 147.2, 141.8, 130.0, 128.7, 128.4, 127.0, 126.9, 126.8, 124.4,
122.8, 121.8, 117.7, 48.4, 24.6 ppm; IR (ATR): 2925, 2854, 1726,
1640, 1598, 1497, 1431, 1325, 1296, 1233, 1186, 1148, 1081, 1026,
890, 858, 751, 691, 655 cmÀ1; HRMS (EI) m/z calcd for C17H14N2 [M+
]: 246.1157; found: 246.1157.
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to give compound 12 (15 mg, 36%) as a pale yellow oil. H NMR
(400 MHz, Chloroform-d): d=7.84 (s, 1H), 7.67–7.65 (m, 2H), 7.64–
7.62 (m, 1H), 7.55–7.51 (m, 1H), 7.47–7.40 (m, 3H), 7.35–7.32 (m,
2H), 4.32 (t, J=8.0 Hz, 2H), 3.30–3.26 ppm (m, 2H); 13C NMR
(100 MHz, Chloroform-d): d=170.0, 155.1, 146.0, 136.0, 132.0,
130.7, 128.8, 128.7, 128.1, 127.5, 127.0, 126.5, 125.7, 124.8, 47.4,
24.6 ppm; IR (ATR): 3058, 2923, 2853, 1630, 1579, 1508, 1477, 1445,
1410, 1360, 1253, 1179, 1152, 1116, 1075, 1024, 956, 906, 877, 784,
757, 721, 697, 661 cmÀ1; HRMS (EI) m/z calcd for C18H14N2O [M+]:
274.1106; found: 274.1104.
Typical procedure for the synthesis of 1-(2-(cyclopropyli-
denemethyl)phenyl)-2,3-dihydro-1H-pyrrolo[2,3-b]quinoline
(10a)
To an oven-dried Schlenk tube that was equipped with a magnetic
stirrer bar were sequentially added 1a (0.25 mmol), 13a
(0.125 mmol), and toluene (1 mL) under a nitrogen atmosphere.
Then, a condenser was fitted and the mixture was stirred at 658C
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Chem. Eur. J. 2016, 22, 1 – 8
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