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Synlett 2013; 24(2): 161-164
DOI: 10.1055/s-0032-1317952
letter
© Georg Thieme Verlag Stuttgart · New York

Copper-Catalyzed Tandem Synthesis of Highly Functionalized Bisamidines

Issa Yavari*
Department of Chemistry, Tarbiat Modares University, PO Box 14115-175 Tehran, Iran   Fax: +98(21)82883455   Email: yavarisa@modares.ac.ir
,
Manijeh Nematpour
Department of Chemistry, Tarbiat Modares University, PO Box 14115-175 Tehran, Iran   Fax: +98(21)82883455   Email: yavarisa@modares.ac.ir
,
Esmat Sodagar
Department of Chemistry, Tarbiat Modares University, PO Box 14115-175 Tehran, Iran   Fax: +98(21)82883455   Email: yavarisa@modares.ac.ir
› Author Affiliations
Further Information

Publication History

Received: 08 October 2012

Accepted after revision: 05 December 2012

Publication Date:
08 January 2013 (online)

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Abstract

The synthesis of a novel class of bisamidines via a copper-catalyzed tandem reaction of trichloroacetonitrile, primary amines, sulfonyl azides, and terminal alkynes is described.

Keywords

bisamidines - ketenimines - tandem reaction - sulfonyl azide - terminal alkyne - trichloroacetonitrile
 

  • References and Notes

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  • 33 Typical Procedure for the Preparation of Compounds 6 The corresponding primary alkylamines 3 (1 mmol) and 4 (0.144 g, 1 mmol) were dissolved in MeCN (2 mL) and stirred for 30 min. Then, a mixture of the sulfonyl azide 2, (1.2 mmol), alkyne 1 (1 mmol), CuI (0.019, 0.1 mmol), and Et3N (0.100 g, 1 mmol) in MeCN (3 mL) was slowly added to the first mixture and was stirred at r.t. under N2 atmosphere. After completion of the reaction [about 8 h; TLC (EtOAc–hexane = 1:5) monitoring], the mixture was diluted with CH2Cl2 (2 mL) and aq NH4Cl solution (3 mL), stirred for 30 min, and the layers were separated. The aqueous layer was extracted with CH2Cl2 (3 × 3 mL), and the combined organic fractions were dried (Na2SO4) and concentrated under reduced pressure. The residue was purified by flash column chromatography [silica gel (230–400 mesh; Merck), hexane–EtOAc = 5:1] to give the product. N′-Benzyl-2,2,2-trichloro-N-[1-(4-methylphenyl-sulfonamido)-2-phenylethylidene]acetimidamide (6a) Cream powder; mp 156–159 °C; yield 0.44 g (84%). IR (KBr): νmax = 3060, 1687, 1592, 1448, 1375, 1178, 1079, 756 cm–1. 1H NMR (500 MHz, CDCl3): δ = 2.47 (3 H, s, Me), 4.25 (2 H, s, CH2), 4.45 (2 H, s, CH2), 7.26–7.32 (3 H, m, Ph), 7.38 (2 H, d, 3 J = 7.4 Hz, Ar), 7.46–7.48 (4 H, m, Ph), 7.58 (1 H, t, 3 J = 7.4 Hz, Ar), 7.89 (2 H, d, 3 J = 7.9 Hz, Ar), 7.97 (2 H, d, 3 J = 7.9 Hz, Ar), 10.08 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 31.5 (Me), 42.2 (CH2), 46.4 (CH2), 90.4 (CCl3), 122.6 (C), 127.5 (2 CH), 128.8 (2 CH), 129.2 (C), 129.3 (2 CH), 129.4 (2 CH), 130.8 (2 CH), 131.0 (CH), 132.5 (2 CH), 134.4 (CH), 142.1 (C), 147.3 (C), 171.7 (C), 176.0 (C). MS: m/z (%) = 521 (2) [M+], 430 (10), 404 (13), 366 (16), 170 (32), 155 (100), 91 (70), 77 (54). Anal. Calcd (%) for C24H22Cl3N3O2S (521.05): C, 55.13; H, 4.24; N, 8.04. Found: C, 55.49; H, 4.30; N, 8.11. N′-Benzyl-2,2,2-trichloro-N-[2-phenyl-1-(phenylsulfonamido)ethylidene]acetimidamide (6b) Cream powder; mp 160–163 °C; yield 0.40 g (80%). IR (KBr): νmax = 3063, 1684, 1590, 1448, 1376, 1273, 1181, 1079, 759 cm–1. 1H NMR (500 MHz, CDCl3): δ = 4.18 (2 H, s, CH2), 4.46 (2 H, s, CH2), 7.25–7.32 (3 H, m, Ph), 7.46–7.49 (4 H, m, Ph), 7.58–7.61 (3 H, m, Ph), 7.71 (1 H, t, 3 J = 7.4 Hz, Ar), 7.96 (2 H, d, 3 J = 7.9 Hz, Ar), 8.03 (2 H, d, 3 J = 7.9 Hz, Ar), 10.68 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 41.5 (CH2), 45.6 (CH2), 90.4 (CCl3), 122.6 (C), 127.4 (2 CH), 128.8 (2 CH), 129.2 (C), 129.3 (2 CH), 129.4 (2 CH), 130.2 (2 CH), 132.6 (2 CH), 134.2 (CH), 134.4 (CH), 135.7 (CH), 144.8 (C), 171.7 (C), 176.0 (C). MS: m/z (%) = 507 (1) [M+], 415 (6), 390 (10), 351 (18), 273 (16), 141 (100), 91 (38), 77 (50). Anal. Calcd (%) for C23H20Cl3N3O2S (507.03): C, 54.29; H, 3.96; N, 8.26. Found: C, 54.61; H, 3.85; N, 8.34. N′-Benzyl-2,2,2-trichloro-N-[1-(methylsulfonamido)-2-phenylethylidene]acetimidamide (6c) Cream powder; mp 142–145 °C; yield 0.33 g (74%). IR (KBr): νmax = 3030, 1687, 1593, 1448, 1369, 1279, 1176, 1071, 751 cm–1. 1H NMR (500 MHz, CDCl3): δ = 3.64 (3 H, s, Me), 4.12 (2 H, s, CH2), 4.45 (2 H, s, CH2), 7.25–7.33 (3 H, m, Ph), 7.47–7.50 (4 H, m, Ph), 7.58 (1 H, t, 3 J = 7.4 Hz, Ar), 7.98 (2 H, d, 3 J = 7.9 Hz, Ar), 10.29 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 31.5 (Me), 43.0 (CH2), 47.0 (CH2), 90.5 (CCl3), 122.5 (C), 128.8 (2 CH), 129.2 (CH), 129.3 (2 CH), 129.4 (2 CH), 130.0 (C), 132.5 (2 CH), 134.4 (CH), 171.7 (C), 176.0 (C). MS: m/z (%) = 445 (2) [M+], 366 (6), 353 (10), 351 (18), 203 (16), 94 (100), 91 (23), 78 (42), 77 (50). Anal. Calcd (%) for C18H18Cl3N3O2S (445.02): C, 48.39; H, 4.06; N, 9.41. Found: C, 48.72; H, 4.15; N, 9.32. 2,2,2-Trichloro-N′-(4-chlorobenzyl)-N-[1-(4-methylphenyl-sulfonamido)-2-phenylethylidene]acetimidamide (6d) Cream powder; mp 169–172 °C; yield 0.43 g (78%). IR (KBr): νmax = 3039, 1633, 1590, 1368, 1218, 1018, 750 cm–1. 1H NMR (500 MHz, CDCl3): δ = 2.46 (3 H, s, Me), 4.18 (2 H, s, CH2), 4.40 (2 H, s, CH2), 7.26–7.34 (3 H, m, Ph), 7.38 (2 H, d, 3 J = 7.9 Hz, Ar), 7.43–7.47 (4 H, m, Ph), 7.88–7.91 (4 H, m, Ph), 10.09 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 31.0 (Me), 42.4 (CH2), 46.2 (CH2), 90.4 (CCl3), 122.5 (C), 127.4 (2 CH), 128.7 (2 CH), 129.2 (C), 129.6 (2 CH), 130.7 (2 CH), 130.8 (2 CH), 132.5 (2 CH), 132.7 (CH), 140.9 (C), 142.1 (C), 147.3 (C), 170.6 (C), 176.0 (C). MS: m/z (%) = 555 (2) [M+], 463 (7), 468 (20), 438 (16), 384 (23), 155 (100), 125 (22), 91 (70), 77 (50). Anal. Calcd (%) for C24H21Cl4N3O2S (555.01): C, 51.72; H, 3.80; N, 7.54. Found: C, 51.29; H, 3.71; N, 7.66. 2,2,2-Trichloro-N′-(4-chlorobenzyl)-N-[2-phenyl-1-(phenylsulfonamido)ethylidene]acetimidamide (6e) Cream powder; mp 149–152 °C; yield 0.39 g (73%). IR (KBr): νmax = 3066, 1680, 1582, 1451, 1377, 1265, 1180, 1078, 758 cm–1. 1H NMR (500 MHz, CDCl3): δ = 4.08 (2 H, s, CH2), 4.40 (2 H, s, CH2), 7.26–7.33 (3 H, m, Ph), 7.43 (2 H, d, 3 J = 7.8 Hz, Ar), 7.46 (2 H, d, 3 J = 7.9 Hz, Ar), 7.59 (2 H, t, 3 J = 7.8 Hz, Ar), 7.71 (1 H, t, 3 J = 7.9 Hz, Ar), 7.91 (2 H, d, 3 J = 8.0 Hz, Ar), 8.02 (2 H, d, 3 J = 8.0 Hz, Ar), 10.29 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 41.0 (CH2), 46.6 (CH2), 90.5 (CCl3), 122.6 (C), 127.4 (2 CH), 128.8 (2 CH), 129.2 (CH), 129.6 (2 CH), 130.1 (2 CH), 130.8 (2 CH), 132.6 (2 CH), 132.7 (C), 135.7 (CH), 140.9 (C), 144.8 (C), 170.6 (C), 176.0 (C). MS: m/z (%) = 541 (2) [M+], 463 (17), 449 (20), 399 (34), 384 (37), 141 (100), 125 (23), 91 (71), 77 (53). Anal. Calcd (%) for C23H19Cl4N3O2S (541.00): C, 50.85; H, 3.52; N, 7.73. Found: C, 51.29; H, 3.45; N, 7.66. 2,2,2-Trichloro-N′-(4-chlorobenzyl)-N-[1-(methyl-sulfonamido)-2-phenylethylidene]acetimidamide (6f) Cream powder; mp 179–182 °C; yield 0.33 g (70%). IR (KBr): νmax = 3063, 1685, 1589, 1449, 1376, 1275, 1181, 1079, 748 cm–1. 1H NMR (500 MHz, CDCl3): δ = 3.65 (3 H, s, Me), 4.07 (2 H, s, CH2), 4.40 (2 H, s, CH2), 7.26–7.34 (3 H, m, Ph), 7.43–7.48 (4 H, m, Ph), 7.90 (2 H, d, 3 J = 8.0 Hz, Ar), 10.10 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 31.0 (Me), 42.0 (CH2), 46.7 (CH2), 90.4 (CCl3), 122.5 (C), 128.8 (2 CH), 129.3 (CH), 129.7 (2 CH), 130.8 (2 CH), 132.5 (2 CH), 132.7 (C), 140.9 (C), 170.7 (C), 176.0 (C). MS: m/z (%) = 478 (2) [M+], 399 (7), 387 (20), 353 (23), 267 (20), 125 (25), 94 (100), 91 (70), 79 (50), 77 (26). Anal. Calcd (%) for C18H17Cl4N3O2S (478.98): C, 44.93; H, 3.56; N, 8.73. Found: C, 44.39; H, 3.47; N, 8.79. 2,2,2-Trichloro-N′-(4-methylbenzyl)-N-[1-(4-methylphenyl-sulfonamido)-2-phenylethylidene]acetimidamide (6g) Cream powder; mp 189–193 °C; yield 0.43 g (81%). IR (KBr): νmax = 3032, 1617, 1592, 1450, 1375, 1222, 1177, 1079, 749 cm–1. 1H NMR (500 MHz, CDCl3): δ = 2.43 (3 H, s, Me), 2.68 (3 H, s, Me), 4.02 (2 H, s, CH2), 4.52 (2 H, s, CH2), 7.29–7.34 (5 H, m, Ph), 7.40 (2 H, d, 3 J = 7.8 Hz, Ar), 7.51 (2 H, d, 3 J = 7.8 Hz, Ar), 7.79 (2 H, d, 3 J = 7.8 Hz, Ar), 7.93 (2 H, d, 3 J = 7.9 Hz, Ar), 10.09 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 32.0 (Me), 35.2 (Me), 41.9 (CH2), 45.6 (CH2), 90.4 (CCl3), 122.6 (C), 127.4 (2 CH), 128.7 (2 CH), 129.2 (CH), 130.1 (2 CH), 130.3 (2 CH), 130.7 (2 CH), 132.5 (2 CH), 134.7 (C), 142.1 (C), 146.0 (C), 147.3 (C), 172.4 (C), 176.0 (C). MS: m/z (%) = 535 (1) [M+], 444 (7), 430 (23), 380 (20), 287 (42), 170 (54), 155 (100), 105 (22), 91 (70), 77 (40). Anal. Calcd (%) for C25H24Cl3N3O2S (535.07): C, 55.93; H, 4.51; N, 7.83. Found: C, 56.35; H, 4.60; N, 7.76. 2,2,2-Trichloro-N′-(4-methylbenzyl)-N-[2-phenyl-1-(phenylsulfonamido)ethylidene]acetimidamide (6h) Cream powder; mp 179–182 °C; yield 0.41 g (78%). IR (KBr): νmax = 3031, 1613, 1592, 1451, 1376, 1220, 1177, 1079, 743 cm–1. 1H NMR (500 MHz, CDCl3): δ = 2.45 (3 H, s, Me), 4.02 (2 H, s, CH2), 4.72 (2 H, s, CH2), 7.31–7.37 (5 H, m, Ph), 7.51 (2 H, d, 3 J = 7.8 Hz, Ar), 7.63 (2 H, t, 3 J = 7.8 Hz, Ar), 7.67 (1 H, t, 3 J = 7.8 Hz, Ar), 7.77 (2 H, d, 3 J = 7.9 Hz, Ar), 8.07 (2 H, d, 3 J = 7.9 Hz, Ar), 9.98 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 32.3 (Me), 42.3 (CH2), 48.3 (CH2), 90.5 (CCl3), 122.6 (C), 127.4 (2 CH), 128.8 (2 CH), 129.3 (CH), 130.2 (2 CH), 130.3 (2 CH), 130.7 (2 CH), 132.6 (2 CH), 134.6 (C), 135.7 (CH), 144.8 (C), 146.0 (C), 172.4 (C), 176.4 (C). MS: m/z (%) = 521 (1) [M+], 430 (7), 415 (20), 380 (23), 273 (25), 141 (100), 91 (72), 77 (52). Anal. Calcd (%) for C24H22Cl3N3O2S (521.05): C, 55.13; H, 4.24; N, 8.04. Found: C, 55.61; H, 4.35; N, 8.16. N′-1-(Benzylimino)-2,2,2-trichloroethyl)-N-tosyl-pentanimidamide (6i) Pale yellow oil; yield 0.34 g (69%). IR (KBr): νmax = 3030, 1679, 1582, 1451, 1376, 1179, 1078, 741 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.98 (3 H, t, 3 J = 6.8 Hz, Me), 1.52–1.59 (2 H, m, CH2), 1.95–1.97 (2 H, m, CH2), 2.50 (3 H, s, Me), 3.21 (2 H, t, 3 J = 6.8 Hz, CH2), 4.47 (2 H, s, CH2), 7.40 (2 H, d, 3 J = 7.8 Hz, Ar), 7.51 (2 H, t, 3 J = 7.8 Hz, Ar), 7.61 (1 H, t, 3 J = 7.8 Hz, Ar), 7.91 (2 H, d, 3 J = 7.9 Hz, Ar), 7.99 (2 H, d, 3 J = 7.9 Hz, Ar), 10.09 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 13.8 (Me), 20.8 (CH2), 22.2 (CH2), 31.4 (Me), 38.4 (CH2), 45.4 (CH2), 90.4 (CCl3), 122.5 (C), 127.4 (2 CH), 129.3 (CH), 129.4 (2 CH), 130.7 (2 CH), 134.4 (2 CH), 142.1 (C), 147.3 (C), 171.6 (C), 176.0 (C). MS: m/z (%) = 487 (1) [M+], 430 (7), 396 (20), 370 (29), 170 (23), 155 (100), 91 (60), 77 (47), 57 (35). Anal. Calcd (%) for C21H24Cl3N3O2S (487.07): C, 51.59; H, 4.95; N, 8.60. Found: C, 51.18; H, 5.06; N, 8.74. N-(Phenylsulfonyl)-N′-2,2,2-trichloro-1-[(4-chlorobenzyl)imino)ethyl]pentanimidamide (6j) Pale yellow oil; yield 0.32 g (64%). IR (KBr): νmax = 3031, 1610, 1494, 1368, 1224, 1173, 1070, 740 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.99 (3 H, t, 3 J = 6.8 Hz, Me), 1.52–1.59 (2 H, m, CH2), 1.94–1.97 (2 H, m, CH2), 3.23 (2 H, t, 3 J = 6.8 Hz, CH2), 4.43 (2 H, s, CH2), 7.47 (2 H, d, 3 J = 7.8 Hz, Ar), 7.63 (2 H, t, 3 J = 7.8 Hz, Ar), 7.76 (1 H, t, 3 J = 7.8 Hz, Ar), 7.92 (2 H, d, 3 J = 7.9 Hz, Ar), 8.06 (2 H, d, 3 J = 7.9 Hz, Ar), 10.10 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 13.8 (Me), 20.8 (CH2), 22.3 (CH2), 37.7 (CH2), 45.5 (CH2), 90.4 (CCl3), 127.4 (2 CH), 129.6 (2 CH), 130.1 (2 CH), 130.8 (2 CH), 132.7 (C), 135.7 (CH), 141.0 (C), 144.8 (C), 170.6 (C), 176.0 (C). MS: m/z (%) = 507 (1) [M+], 449 (7), 382 (20), 366 (27), 155 (100), 141 (34), 125 (22), 91 (70), 77 (30), 57 (21). Anal. Calcd (%) for C20H21Cl4N3O2S (507.01): C, 47.17; H, 4.16; N, 8.25. Found: C, 47.49; H, 4.27; N, 8.36. N′-1-[(Benzylimino)-2,2,2-trichloroethyl]-N-tosylhexanimidamide (6k) Pale yellow oil; yield: 0.30 g (60%). IR (KBr): νmax = 3032, 1685, 1592, 1372, 1278, 1187, 1072, 739 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.93 (3 H, t, 3 J = 6.8 Hz, Me), 1.41–1.48 (2 H, m, CH2), 1.50–1.55 (2 H, m, CH2), 1.93–1.96 (2 H, m, CH2), 2.50 (3 H, s, Me), 3.22 (2 H, t, 3 J = 6.8 Hz, CH2), 4.48 (2 H, s, CH2), 7.41 (2 H, d, 3 J = 7.8 Hz, Ar), 7.50 (2 H, t, 3 J = 7.8 Hz, Ar), 7.62 (1 H, t, 3 J = 7.8 Hz, Ar), 7.92 (2 H, d, 3 J = 7.9 Hz, Ar), 7.99 (2 H, d, 3 J = 7.9 Hz, Ar), 10.10 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 14.0 (Me), 18.5 (CH2), 22.2 (CH2), 24.4 (CH2), 31.0 (Me), 39.9 (CH2), 46.0 (CH2), 90.4 (CCl3), 122.5 (C), 127.4 (2 CH), 129.2 (2 CH), 129.4 (2 CH), 130.7 (2 CH), 134.4 (CH), 142.1 (C), 147.3 (C), 171.6 (C), 176.0 (C). MS: m/z (%) = 501 (1) [M+], 430 (7), 410 (20), 346 (42), 170 (32), 155 (100), 91 (25), 71 (50). Anal. Calcd (%) for C22H26Cl3N3O2S (501.08): C, 52.54; H, 5.21; N, 8.36. Found: C, 52.29; H, 5.30; N, 8.42. N′-1-[(Benzylimino)-2,2,2-trichloroethyl]-N-(methylsulfonyl)hexanimidamide (6l) Pale yellow oil; yield: 0.24 g (57%). IR (KBr): νmax = 3030, 1679, 1451, 1376, 1265, 1179, 1078, 742 cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.93 (3 H, t, 3 J = 6.8 Hz, Me), 1.42–1.49 (2 H, m, CH2), 1.51–1.55 (2 H, m, CH2), 1.94–1.96 (2 H, m, CH2), 3.24 (2 H, t, 3 J = 6.8 Hz, CH2), 3.63 (3 H, s, Me), 4.48 (2 H, s, CH2), 7.50 (2 H, t, 3 J = 7.7 Hz, Ar), 7.61 (1 H, t, 3 J = 7.7 Hz, Ar), 7.99 (2 H, d, 3 J = 7.7 Hz, Ar), 10.08 (1 H, s, NH). 13C NMR (125.7 MHz, CDCl3): δ = 13.9 (Me), 18.5 (CH2), 22.3 (CH2), 25.4 (CH2), 31.5 (Me), 39.9 (CH2), 46.1 (CH2), 90.4 (CCl3), 122.5 (C), 129.3 (2 CH), 129.4 (2 CH), 134.4 (CH), 171.7 (C), 176.0 (C). MS: m/z (%) = 425 (1) [M+], 353 (7), 346 (20), 334 (34), 308 (21), 94 (100), 91 (28), 78 (65), 71 (50). Anal. Calcd (%) for C16H22Cl3N3O2S (425.05): C, 45.03; H, 5.20; N, 9.85. Found: C, 45.49; H, 5.29; N, 9.76.
  • 34 Recently, Sharpless and co-workers established anhydrous conditions with CuI in CHCl3–2,6-lutidine at 0 °C to prevent intermediate 8 from decomposing and provide selective formation of the desired 1-sulfonyltriazoles. See: Yoo EJ, Ahlquist M, Kim SH, Bae I, Fokin VV, Sharpless KB, Chang S. Angew. Chem. Int. Ed. 2007; 46: 1730
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  • 35 Cassidy MP, Raushel J, Fokin VV. Angew. Chem. Int. Ed. 2006; 45: 3154
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  • 36 Yoo EJ, Ahlquist M, Bae I, Sharpless KB, Fokin VV, Chang S. J. Org. Chem. 2008; 73: 5520
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