PAPER
Sequential Sonogashira and Suzuki Cross-Coupling Reactions
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126.8 (d), 127.4 (d), 129.2 (s), 129.6 (d), 130.0 (d), 130.3 (d), 133.9
(s), 134.7 (s), 136.8 (s), 143.8 (s), 145.4 (s).
N-[3-(1-Benzenesulfonyl-5-methoxy-1H-indol-3-yl)-prop-2-
ynyl]-4-methyl-benzenesulfonamide (4g)
Yield: 96%; yellow crystals; mp 153 °C (CHCl3–pentane).
MS (EI, 70 eV): m/z (%) = 477 (5) [M+], 423 (8), 367 (24), 323 (27),
258 (36), 231 (18), 168 (100), 141 (57), 91 (86).
IR (KBr): 3251, 1612, 1475, 1445, 1377, 1327, 1291, 1249, 1215,
1163, 1124, 1094, 1029, 988, 942, 846, 816, 723, 684, 601 cm–1.
1H NMR (200 MHz; CDCl3): d = 2.27 (s, 3 H), 3.85 (s, 3 H), 4.15
(d, J = 6.0 Hz, 2 H), 4.92 (t, J = 6.0 Hz, 1 H), 6.84 (d, J = 2.4 Hz, 1
H), 6.98 (dd, J = 2.2, 9.1 Hz, 1 H), 7.24 (d, J = 8.5 Hz, 2 H), 7.43–
7.64 (m, 4 H), 7.82–7.90 (m, 5 H).
Anal. Calcd for C25H22N2O4S2 (477.6): C, 62.81; H, 4.61; N, 5.86.
Found: C, 62.45; H, 4.57; N, 5.78.
3-(3-Dimethylamino-prop-1-ynyl)-5-methoxy-indole-1-carbox-
ylic Acid tert-Butyl Ester (4d)
Yield: 97%; yellow crystals; mp 69–70 °C (CHCl3–pentane).
13C NMR (50 MHz, CDCl3): d = 21.7 (q), 34.4 (t), 56.2 (q), 76.5 (s),
88.2 (s), 102.9 (d), 104.7 (s), 114.9 (d), 115.4 (d), 127.2 (d), 127.9
(d), 129.0 (s), 129.8 (d), 130.1 (d), 130.2 (d), 131.9 (s), 134.6 (d),
137.2 (s), 138.2 (s), 144.4 (s), 157.3 (s).
MS (EI, 70 eV): m/z (%) = 494 (56) [M+], 429 (7), 401 (7), 338 (38),
311 (21), 289 (33), 260 (31), 214 (30), 197 (51), 183 (33), 170 (89),
155 (54), 91 (100), 78 (31).
IR (KBr): 2937, 2781, 1728, 1615, 1479, 1451, 1378, 1330, 1289,
1245, 1156, 1090, 1036, 1017, 853, 807, 764 cm–1.
1H NMR (400 MHz, CDCl3): d = 1.65 (s, 9 H), 2.40 (s, 6 H), 3.55
(s, 2 H), 3.87 (s, 3 H), 6.95 (dd, J = 9.0, 2.6 Hz, 1 H), 7.10 (d, J =
2.6 Hz, 1 H), 7.70 (s, 1 H), 7.99 (d, J = 9.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 28.1 (q), 44.2 (q), 48.8 (t), 55.7
(q), 76.9 (s), 84.0 (s), 87.9 (s), 102.3 (d), 103.1 (s), 114.0 (d), 116.0
(d), 129.2 (d), 131.5 (s), 149.0 (s), 156.3 (s).
Anal. Calcd for C25H22N2O5S2 (494.58): C, 60.71; H, 4.48; N, 5.66.
Found: C, 60.48; H, 4.48; N, 5.66.
MS (EI, 70 eV): m/z (%) = 328 (63) [M+], 272 (74), 227 (100), 213
(52), 184 (96), 113 (7).
3-(1-Benzenesulfonyl-5-methoxy-1H-indol-3-yl)-prop-2-yn-1-ol
(4h)
Yield: 91%; yellow crystals; mp 179–180 °C (CHCl3–pentane).
Anal. Calcd for C19H24N2O3 (327.7): C, 69.58; H, 7.32; N, 8.54.
Found: C, 69.43; H, 7.40; N, 8.47.
IR (KBr): 3565, 3117, 1610, 1482, 1447, 1364, 1313, 1290, 1251,
1212, 1175, 1147, 1127, 1097, 1025, 991, 970, 841, 812, 759, 725,
690, 610, 582 cm–1.
1H NMR (400 MHz, CDCl3): d = 1.80 (br s, 1 H), 3.84 (s, 3 H), 4.56
(s, 2 H), 6.96 (dd, J = 9.0, 2.6 Hz, 1 H), 7.02 (d, J = 2.4 Hz, 1 H),
7.42–7.45 (m, 2 H), 7.54 (tt, J = 7.5, 1.2 Hz, 1 H), 7.69 (s, 1 H) 7.84–
7.87 (m, 3 H).
13C NMR (100 MHz, CDCl3): d = 51.8 (t), 55.7 (q), 76.9 (s), 91.7
(s), 102.3 (d), 104.7 (s), 114.5 (d), 115.1 (d), 126.8 (d), 128.8 (s),
129.4 (d), 129.9 (d), 131.7 (s), 134.1 (d), 137.8 (s), 157.0 (s).
3-(2-Pyrrolidinocarboxy-prop-1-ynyl)-5-methoxy-indole-1-car-
boxylic Acid tert-Butyl Ester (4e)
Yield: 93%; white crystals; mp 166–167 °C (petroleum ether–
Et2O).
IR (KBr): 2975, 2932, 2875, 1750, 1628, 1482, 1450, 1394, 1332,
1249, 1155, 1091, 1035, 1020, 853, 798, 762 cm–1.
1H NMR (400 MHz, CDCl3): d = 1.66 (s, 9 H), 1.96–2.04 (m, 4 H),
3.56 (t, J = 6.3 Hz, 2 H), 3.80 (t, J = 6.4 Hz, 2 H), 3.88 (s, 3 H), 6.98
(dd, J = 9.0, 2.3 Hz, 1 H), 7.11 (d, J = 2.3 Hz, 1 H), 7.89 (s, 1 H),
8.02 (d, J = 8.6 Hz, 1 H).
MS (EI, 70 eV): m/z (%) = 341 (100) [M+], 200 (57), 185 (51), 170
(54), 157 (60), 134 (15), 78 (25).
13C NMR (100 MHz, CDCl3): d = 24.9, 25.6, 28.3, 45.6, 48.4, 55.9,
82.1, 84.9, 86.8, 100.8, 102.6, 114.7, 116.4, 129.4, 131.1, 132.2,
153.1, 156.8.
Anal. Calcd for C18H15NO4S (341.38): C, 63.32; H, 4.42; N, 4.10.
Found: C, 63.22; H, 4.55; N, 4.13.
MS (EI, 70 eV): m/z (%) = 368 (42) [M+], 312 (100), 268 (70), 239
(30), 198 (55), 170 (14).
5-Methoxy-3-phenylethynyl-1-(toluene-4-sulfonyl)-1H-indole
(4i)
Yield: 76%; brown crystals; mp 127–128 °C (CHCl3–pentane).
Anal. Calcd for C21H24N2O4 (368.44): C, 68.46; H, 6.57; N, 7.90.
Found: C, 68.29; H, 6.68; N, 7.81.
IR (KBr): 3124, 1611, 1476, 1445, 1371, 1301, 1214, 1164, 1118,
1093, 1028, 976, 892, 818, 758, 679, 589 cm–1.
1H NMR (400 MHz, CDCl3): d = 2.29 (s, 3 H), 3,80 (s, 3 H), 6,92
(dd, J = 9.0, 2.4 Hz, 1 H), 7.05 (d, J = 2.4 Hz, 1 H), 7.18 (d, J = 8.6
Hz, 2 H), 7.30–7.32 (m, 3 H), 7.49–7.52 (m, 2 H), 7.70–7.72 (m, 3
H), 7.82 (d, J = 9.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 21.5 (q), 55.7 (q), 80.4 (s), 93.6
(s), 102.6 (d), 105.2 (s), 114.6 (d), 114.8 (d), 123.0 (s), 126.8 (d),
128.38 (s), 128.40 (d), 128.9 (d), 129.4 (d), 129.9 (d), 131.5 (d)
131.8 (s), 134.9 (s), 145.2 (s), 156.9 (s).
[3-(1-Benzenesulfonyl-5-methoxy-1H-indol-3-yl)-prop-2-ynyl]-
dimethyl-amine (4f)
Yield: 94%; pale yellow crystals; mp 84–85 °C (CHCl3–pentane).
IR (KBr): 3198, 3187, 2768, 1610, 1482, 1445, 1378, 1294, 1248,
1215, 1176, 1128, 1085, 1032, 994, 856, 818, 726, 685, 612, 582
cm–1.
1H NMR (400 MHz, CDCl3): d = 2.32 (s, 6 H), 3.47 (s, 2 H), 3.76
(s, 3 H), 6.89 (dd, J = 2.6, 9.0 Hz, 1 H), 6.97 (d, J = 2.1 Hz, 1 H),
7.31–7.51 (m, 3 H), 7.60 (s, 1 H), 7.77–7.81 (m, 3 H).
13C NMR (100 MHz, CDCl3): d = 44.7 (q), 49.2 (t), 56.1 (q), 76.5
(s), 89.5 (s), 103.0 (d), 105.8 (s), 114.9 (d), 115.2 (d), 127.2 (d),
129.3 (s), 129.77 (d), 129.79 (d), 132.5 (s), 134.4 (d), 138.3 (s),
157.3 (s).
MS (EI, 70 eV): m/z (%) = 401 (57) [M+], 246 (100), 231 (25), 203
(18), 176 (9), 82 (11).
Anal. Calcd for C24H19NO3S (401.48): C, 71.74; H, 4.76; N, 3.48.
Found: C, 71.41; H, 4.74; N, 3.43.
MS (EI, 70 eV): m/z (%) = 368 (53) [M+], 324 (37), 227 (100), 212
(34), 183 (93), 168 (25), 146 (15), 78 (13).
5-Bromo-3-[3-(toluene-4-sulfonylamino)-prop-1-ynyl]-indole-
1-carboxylic Acid tert-Butyl Ester (4j)
Yield: 91%; pale yellow crystals; mp 147–148 °C (CHCl3–pen-
tane).
Anal. Calcd for C20H20N2O3S (368.45): C, 65.19; H, 5.47; N, 7.60.
Found: C, 65.10; H, 5.51; N, 7.59.
IR (KBr): 3280, 2970, 1721, 1600, 1453, 1426, 1383, 1343, 1285,
1270, 1228, 1165, 1116, 1094, 1055, 892, 862, 814, 798, 670 cm–1.
Synthesis 2005, No. 5, 771–780 © Thieme Stuttgart · New York