C. Koradin et al. / Tetrahedron 59 (2003) 1571–1587
1581
gel (pentane/ether 9:1) to afford 2i (80 mg, 0.22 mmol,
80%) as a yellow solid. Mp: 145–1468C. 1H NMR (CD2Cl2,
300 MHz): d¼8.93 (s, br, 1H), 7.92 (s, br, 1H), 7.80–7.74
(m, 2H), 7.70–7.62 (m, 3H), 7.54–7.40 (m, 6H), 6.97 (m,
1H). 13C NMR (CD2Cl2, 75 MHz): d¼140.3, 138.6, 131.8,
131.3, 129.2, 129.0, 128.7, 128.6, 128.5, 125.6, 123.0, 122.6,
122.2, 122.1, 118.5 (q), 106.7, 101.2, 94.5, 84.0. IR (KBr):
3465 (vs), 1630 (s), 1490 (m), 1367 (s), 1317 (m), 1282 (s),
1111 (s), 749 (s). m/z (EI,%): 361 (Mþ, 100), 342 (3), 291 (4).
HRMS: calcd for C23H14F3N 361.1078, found 361.1064.
122.5, 122.4, 120.9, 109.9, 98.6, 59.9, 25.5, 25.1, 22.1, 21.8,
14.1. IR (KBr): 3370 (s), 2937 (w), 1683 (s), 1610 (w), 1471
(w), 1367 (w), 1310 (s), 1258 (m), 1166 (m), 1095 (w), 768
(m). m/z (EI,%): 269 (Mþ, 100), 254 (5), 241 (19), 224 (20),
196 (20), 168 (20), 154 (5), 105 (4). HRMS: calcd for
C17H19NO2 269.1416, found 269.1413.
4.3.13. 5-Methyl-2-phenyl-1H-pyrrolo[2,3-b]pyridine
(2m). The reaction was carried out according to typical
procedure F with KH (40 mg, 1.00 mmol) and 5-methyl-3-
(phenylethynyl)-2-pyridinylamine (100 mg, 0.48 mmol) in
NMP (5 mL) at rt for 1 h. The crude product was purified by
column chromatography on silica gel (pentane/ethyl acetate
1:1) to afford 2m (72 mg, 0.35 mmol, 72%) as a white solid.
Mp: 252–2538C. 1H NMR (DMSO-d6, 300 MHz): d¼11.98
(s, br, 1H), 8.09–8.04 (m, 1H), 7.95–7.89 (m, 2H), 7.70 (s,
1H), 7.45 (t, J¼7.6 Hz, 1H), 7.36–7.29 (m, 1H), 6.82 (s,
1H), 2.36 (s, 3H). 13C NMR (DMSO-d6, 75 MHz):
d¼148.2, 143.6, 138.2, 131.6, 128.8, 127.7, 127.5, 125.1,
124.3, 120.7, 96.4, 18.0. IR (KBr): 3436 (s), 3152 (w), 2914
(w), 1637 (m), 1484 (w), 1456 (m), 1281 (m), 753 (vs), 690
(m). m/z (EI,%): 208 (Mþ, 100), 180 (6), 152 (4), 104 (6).
HRMS: calcd for C14H12N2 208.1000, found 208.0995.
4.3.10. 7-Nitro-2-phenyl-5-(trifluoromethyl)-1H-indole
(2j). The reaction was carried out according to typical
procedure F with KH (72 mg, 1.80 mmol) and 2-nitro-6-
(phenylethynyl)-4-trifluoromethyl)aniline (306 mg, 1.00
mmol) in NMP (5 mL) at rt for 2 h. The crude product
was purified by column chromatography on silica gel
(CH2Cl2 100%) to afford 2j (157 mg, 0.51 mmol, 51%) as a
yellow solid. Mp: 181–1828C. 1H NMR (CDCl3/DMSO-d6,
300 MHz): d¼10.31 (s, br, 1H), 8.31 (s, 1H), 8.14 (s, 1H),
7.74–7.68 (m, 2H), 7.51–7.36 (m, 3H), 6.97 (d, J¼2.4 Hz,
1H). 13C NMR (CDCl3/DMSO-d6, 75 MHz): d¼142.5,
132.3, 131.6, 131.5, 130.3, 129.5, 128.6, 128.3, 128.1,
127.7, 125.7, 123.5 (q, J¼3.9 Hz), 114.5 (q, J¼3.9 Hz),
100.6. IR (KBr): 3414 (m), 2925 (w), 1636 (w), 1524 (m),
1332 (s), 1309 (s), 1269 (m), 1167 (m), 1122 (m), 1085 (w),
894 (w), 758 (m), 588 (w). m/z (EI,%): 306 (Mþ, 100), 287
(37), 276 (14), 206 (31). HRMS: calcd for C15H9F3N2O2
306.0616, found 306.0611.
4.3.14. 2-Phenyl-1H-pyrrolo[3,2-b]pyridine (2n).33 The
reaction was carried out according to typical procedure F
with KH (42 mg, 1.05 mmol) and 2-(phenylethynyl)-3-
pyridinylamine (100 mg, 0.52 mmol) in NMP (5 mL) at rt
for 1 h. The crude product was purified by column
chromatography on silica gel (pentane/ethyl acetate 1:1)
to afford 2n (74 mg, 0.38 mmol, 74%) as a yellow solid.
Mp: 254–2558C. 1H NMR (DMSO-d6, 300 MHz): d¼11.78
(s, br, 1H), 8.32 (dd, J¼4.6, 1.3 Hz, 1H), 7.96–7.91 (m,
2H), 7.77–7.73 (m, 1H), 7.54–7.46 (m, 1H), 7.41–7.34 (m,
1H), 7.13–7.05 (m, 2H). 13C NMR (DMSO-d6, 75 MHz):
d¼146.9, 142.8, 140.8, 131.5, 129.8, 128.9, 128.2, 125.3,
118.0, 116.5, 99.1. IR (KBr): 3436 (vs), 3058 (vw), 1634
(m), 1460 (m), 1416 (s), 1278 (m), 763 (m). m/z (EI,%): 194
(Mþ, 100), 166 (9), 139 (4), 128 (2), 102 (3), 97 (6). HRMS:
calcd for C13H10N2 194.0844, found 194.0839.
4.3.11. Ethyl 2-phenyl-1H-indole-5-carboxylate (2k). The
reaction was carried out according to typical procedure F
with KH (72 mg, 1.80 mmol) and ethyl 4-amino-3-(phenyl-
ethynyl)benzoate (265 mg, 1.00 mmol) in NMP (5 mL) at rt
for 2 h. The crude product was purified by column
chromatography on silica gel (CH2Cl2 100%) to afford 2k
(207 mg, 0.78 mmol, 78%) as a white solid. Mp: 184–
1858C. 1H NMR (CDCl3/DMSO-d6, 300 MHz): d¼11.01 (s,
br, 1H), 8.26 (s, 1H), 7.76–7.70 (m, 3H), 7.37–7.30 (m,
3H), 7.22 (t, J¼7.2 Hz, 1H), 6.78 (d, J¼1.4 Hz, 1H), 4.29
(q, J¼7.2 Hz, 2H), 1.33 (t, J¼7.2 Hz, 3H). 13C NMR
(CDCl3/DMSO-d6, 75 MHz): d¼167.2, 139.4, 139.2, 131.6,
128.3, 128.0, 127.2, 124.9, 122.5, 122.4, 121.2, 110.4, 99.4,
59.8, 13.9. IR (KBr): 3332 (s), 2985 (w), 1686 (vs), 1612 (m),
1461 (w), 1369 (m), 1330 (m), 1296 (m), 1262 (s), 1177 (s),
1096 (w), 1027 (w), 762 (s), 696 (w). m/z (EI,%): 265 (Mþ,
100), 250(6), 237(37),220(60),192(32), 165(18),110(6), 95
(8). HRMS: calcd for C17H15NO2 265.1103, found 265.1101.
4.3.15. 2-Butyl-4-methyl-1H-pyrrolo[3,2-c]quinoline
(2o). The reaction was carried out according to typical
procedure F with KH (48 mg, 1.20 mmol) and 3-(1-
hexynyl)-2-methyl-4-quinolinylamine (190 mg, 0.80 mmol)
inNMP (8 mL) at808C for 6 h. Thecrudeproduct waspurified
by column chromatography on silica gel (pentane/ethyl
acetate 1:2 to ethyl acetate 100%) to afford 2o (171 mg,
0.82 mmol, 82%) as an orange-yellow solid. Mp: 198–2008C
(decomp.). 1H NMR (CDCl3, 300 MHz): d¼10.46 (s, br, 1H),
8.11 (d, J¼8.3 Hz, 1H), 8.06 (d, J¼8.3 Hz, 1H), 7.48 (t,
J¼7.5 Hz, 1H), 7.40 (t, J¼7.1 Hz, 1H), 6.48 (s, 1H), 2.98–
2.80 (m, 5H), 1.73 (quint, J¼7.5 Hz, 2H), 1.39 (sext,
J¼7.4 Hz, 2H), 0.91 (t, J¼7.3 Hz, 3H). 13C NMR (CDCl3,
75 MHz): d¼153.8, 143.2, 139.5, 134.7, 128.4, 126.1, 124.9,
121.1, 119.9, 117.0, 100.1, 31.5, 27.9, 22.3, 22.3, 13.8. IR
(KBr): 3430(s), 3056(w), 2955(m), 2928(m), 1596(m), 1568
(m), 1514 (m), 1366 (vs), 762 (s). m/z (EI,%): 238 (Mþ, 53),
195 (100), 167 (6), 154 (3), 127 (4), 77 (2). HRMS: calcd for
C16H18N2 238.1470, found 238.1472.
4.3.12. Ethyl 2-(1-cyclohexen-1-yl)-1H-indole-5-car-
boxylate (2l). The reaction was carried out according to
typical procedure F with KH (72 mg, 1.80 mmol) and ethyl
4-amino-3-(1-cyclohexen-1-ylethynyl)benzoate (269 mg,
1.00 mmol) in NMP (5 mL) at rt for 2 h. The crude product
was purified by column chromatography on silica gel
(CH2Cl2 100%) to afford 2l (194 mg, 0.72 mmol, 72%) as a
white solid. Mp: 192–1938C. 1H NMR (CDCl3/ DMSO-d6,
300 MHz): d¼10.06 (s, br, 1H), 8.13 (s, 1H), 7.66 (dd,
J¼8.7, 1.5 Hz, 1H), 7.19 (d, J¼8.7 Hz, 1H), 6.31 (d,
J¼1.5 Hz, 1H), 6.19–6.16 (m, 1H), 4.22 (q, J¼7.2 Hz, 2H),
2.34–2.27 (m, 2H), 2.13–2.06 (m, 2H), 1.69–1.49 (m, 4H),
1.26 (t, J¼7.2 Hz, 3H). 13C NMR (CDCl3/DMSO-d6,
75 MHz): d¼167.5, 141.1, 139.1, 128.4, 127.9, 123.4,
4.3.16. 2,6-Diphenyl-1,7-dihydrodipyrrolo[2,3-b:3,2-
e]pyridine (2p). The reaction was carried out according to