The Journal of Organic Chemistry
Page 20 of 38
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IR (KBr, cm-1) 3300, 3136, 2956, 2925, 2858, 1677, 1645, 1604, 1573, 1539, 1480, 1419, 1362,
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1330, 1302, 1282, 1234, 1170, 1092, 1068, 1026, 962, 905, 816, 748, 716, 676, 585, 536; H
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NMR (600 MHz, DMSO) 0.78 (3H, t, J = 6.2 Hz), 1.13-1.16 (3H, m), 1.17-1.24 (3H, m), 2.36
(2H, t, J = 7.6 Hz), 2.51 (3H, s), 3.96 (2H, s), 5.22 (2H, s), 7.19-7.24 (7H, m), 7.39 (1H, s), 7.44
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(2H, d, J = 8.2 Hz), 7.65 (2H, d, J = 9.0 Hz), 8.13 (2H, d, J = 13.8 Hz); C NMR (125 MHz,
DMSO) 13.8 (q), 21.1 (q), 21.7 (t), 24.4 (t), 27.9 (t), 30.0 (t), 31.1 (t), 37.3 (t), 119.7 (s), 121.5
(d), 122.3 (s), 126.5 (d × 2), 126.6 (d × 2), 128.8 (d × 2), 130.3 (d × 2), 130.4 (d × 2), 133.9 (s),
135.2 (s), 135.4 (s), 145.4 (s), 149.3 (s), 152.4 (d), 155.9 (s); EIMS m/z 560 (small M+), 451 (M+-
SPh), 405 (M+-Ts). MS (ESI) m/z 561 [M+H]+; HRMS (ESI-DART) m/z: [M+Na]+ calcd for
C29H33N6O2S2 561.21064; Found 561.20937. Anal. Calcd for C29H32N6O2S2 (+ 2 H2O): C,
58.37; H, 6.08; N, 14.08. Found: C, 58.45; H, 5.76; N, 13.64.
4-[7-(N6,N6-Bis(Boc)amino)-9H-purin-9-yl]methyl-5-phenyl-3-(phenylsulfanylmethyl)-1-
tosylpyrrole (14b), entry 11.
To a DMSO (0.50 mL) solution of 4-methyl-N-[3-(phenylsulfanyl)-2-propyn-1-yl]-N-(1-phethyl-
2-propyn-1-yl)benzenesulfonamide (6) (50 mg, 0.1 mmol) were added 4-[N6,N6-bis(Boc)amino]-
9H-purine (100.6 mg, 0.3 mmol), bis(hexafluoroacetylacetonato)nickel (II) hydrate (9.5 mg, 0.02
mmol), and DBU(45.7 mg, 0.3 mmol). The reaction mixture was stirred for 9.5 h at 50 oC. The
cooled mixture was poured into water (50 mL). The workup procedure gave the titled compound
15b (5 mg, 6%) as pale yellow powders (mp 80-83 oC).
IR (KBr, cm-1) 2925, 2853, 1751, 1609, 1466, 1369, 1323, 1232, 1175, 1146, 1093, 972, 814,
791, 751, 701, 668, 583, 543; 1H NMR (600 MHz, CDCl3) 1.57 (18H, s), 2.38 (3H, s), 3.58 (2H,
s), 5.43 (2H, s), 6.81 (2H, d, J = 6.9 Hz), 7.02 (2H, d, J = 6.9 Hz), 7.10 (2H, d, J = 8.2 Hz), 7.12-
7.17 (4H, m), 7.22 (2H, t, J = 7.6 Hz), 7.35 (1H, t, J = 7.6 Hz), 7.44 (1H, s), 7.97 (1H, brs), 7.99
(1H, s), 8.74 (1H, s); MS (ESI) m/z 789 [M+Na]+, 805 [M+K]+; HRMS (ESI-DART) m/z:
[M+Na]+ calcd for C40H42N6NaO6S2 789.25049; Found 789.24628.
4-[7-(N6,N6-Bis(Boc)amino)-9H-purin-9-yl]methyl-3-(phenylsulfanylmethyl)-1-(p-
nitrophenylsulfonyl)pyrrole (17b), entry 12.
To a DMSO (0.50 mL) solution of 4-nitro-N-[3-(phenylthio)-2-propyn-1-yl]-N-2-propyn-1-
ylbenzenesulfonamide (8) (30 mg, 0.08 mmol) were added 9-[N6,N6-bis(Boc)amino]-9H-purine
(80.5 mg, 0.24 mmol), bis(hexafluoroacetylacetonato)nickel (II) hydrate (4.2 mg, 0.008 mmol),
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and DBU (36.5 mg, 0.24 mmol). The reaction mixture was stirred for 1.0 h at 50 C. The
workup procedure gave the title compound 17b (32 mg, 63%) as pale yellow powders (mp 69-71
oC).
IR (KBr, cm-1) 3106, 2981, 2928, 2853, 1789, 1720, 1604, 1577, 1535, 1453, 1370, 1349, 1280,
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1250, 1211, 1183, 1141, 1108, 1067, 1108, 1067, 953, 854, 741, 683, 629, 586; H NMR (600
MHz, CDCl3) 1.46 (18H, s), 3.86 (2H, s), 5.33 (2H, s), 6.89 (1H, d, J = 2.0 Hz), 7.15 (1H, d, J
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