One-Pot Diastreoselective Synthesis of Highly Functionalized Cyclohexenones

Supporting Information

One-pot diastreoselective synthesis of highly functionalized cyclohexenones: 2-oxo-N,4,6-triarylcyclohex-3-enecarboxamides

Mir RasulMousavi, MalekTaherMaghsoodlou*, Sayyed Mostafa Habibi-Khorassani

Department of Chemistry, The University of Sistan and Baluchestan, P. O. Box 98135-674, Zahedan, Iran

*Corresponding author; tel/ fax: +98-541-2450995

E-mail:

Table of Contents

1. Thespectral and analytical data of highly functionalized cyclohexenones4a-k.

2. NMR (1H and 13C) and Mass spectraof highly functionalized cyclohexenones4a-k.(Figures 1-33)

1. Thespectral and analytical data of highly functionalized cyclohexenones4a-k:

6-(2-bromophenyl)-2-oxo-N,4-diphenylcyclohex-3-enecarboxamide (4a)

White solid, yield: (99%); mp 220-222 ºC. IR (KBr) (νmax/cm-1): 3411, 1676, 1629, 1601, 1557, 1445, 1370, 1248, 1181, 757, 693. 1H NMR (400 MHz, DMSO): 3.01(s, 2H, H-5), 4.20 (d, J = 13.2 Hz, 1H, H-1), 4.26 (dd, J = 5.2, 9.6 Hz, 1H, H-6), 6.63 (s, 1H, H-3), 7.01 (t, J = 7.2 Hz, 1H, Ar-H), 7.17 (t, J = 7.2 Hz, 1H, Ar-H), 7.24 (t, J = 7.6 Hz, 2H, Ar-H), 7.40 (t, J = 7.6 Hz, 1H, Ar-H), 7.46 (d, J = 6.0 Hz, 5H, Ar-H), 7.62 (dd, J = 11.6, 8.0 Hz, 2H, Ar-H), 7.72 (d, J = 7.6 Hz, 2H, Ar-H), 10.21 (s, 1H, NH).13C NMR (100 MHz, DMSO): δ 34.8, 42.2, 58.7, 119.5, 123.8, 123.9, 124.5, 126.8, 128.2, 128.5, 129.1, 129.3, 129.4, 131.0, 133.4, 137.6, 139.1, 141.1, 158.7, 167.3, 195.7.MS (EI, 70 eV) m/z (%): 447 (M++1, 19), 366 (98), 327 (20), 298 (1), 273 (19), 247 (31), 215 (19), 183 (8), 157 (17), 115 (44), 93 (100), 65 (18). Anal. Calcdfor C25H20BrNO2: C, 67.27; H, 4.52; N, 3.14. Found: C, 67.40; H, 4.64; N, 3.22.

6-(3-nitrophenyl)-2-oxo-N,4-diphenylcyclohex-3-enecarboxamide (4b)

Pale yellow solid, yield: (98%); mp 200-202 ºC. IR (KBr) (νmax/cm-1): 3413, 1632, 1601, 1558, 1531, 1445, 1353, 758, 689. 1H NMR (400 MHz, CDCl3): 3.08 (dd, J = 8.4, 18.0 Hz, 1H, H-5), 3.38 (dd, J = 18.2, 4.8 Hz, 1H, H'-5), 3.76 (d, J = 8.8 Hz, 1H, H-1), 4.32 (dd, J = 13.1, 8.8 Hz, 1H, H-6), 6.63 (s, 1H, H-3), 7.10 (t, J = 7.6 Hz, 1H, Ar-H), 7.28 (dd, J = 9.2, 5.2 Hz, 2H, Ar-H), 7.45 (d, J = 2.4 Hz, 2H, Ar-H), 7.48 (d, J = 7.2 Hz, 3H, Ar-H), 7.52 (d, J = 8.0 Hz, 1H, Ar-H), 7.57 (t, J = 6.4 Hz, 2H, Ar-H), 7.69 (d, J = 7.6 Hz, 1H, Ar-H), 8.13 (d, J = 8.4 Hz, 1H, Ar-H), 8.19(s, 1H, Ar-H), 8.25 (s, 1H, NH).13C NMR (100 MHz, CDCl3): δ 33.8, 41.0, 58.5, 120.0, 122.0, 122.3, 124.4, 124.6, 126.3, 128.9, 129.0, 129.8, 131.0, 134.2, 137.3, 137.3 148.5, 159.6, 164.4, 194.5.MS (EI, 70 eV) m/z (%): 412 (M+, 29), 369 (1), 344 (1), 320 (9), 293 (87), 270 (1), 246 (16), 224 (1), 202 (30), 176 (39), 144 (27), 115 (69), 93 (100), 65 (24). Anal. Calcdfor C25H20N2O4: C, 72.80; H, 4.89; N, 6.79. Found: C, 72.86; H, 4.96; N, 6.85.

6-(2-chlorophenyl)-2-oxo-N,4-diphenylcyclohex-3-enecarboxamide (4c)

White solid, yield: (97%); mp 224-226 ºC. IR (KBr) (νmax/cm-1): 3383, 3084, 1674, 1627, 1601, 1559, 1445, 1249, 1180, 757, 693. 1H NMR (400 MHz, DMSO): 3.03 (d, J = 7.2 Hz, 2H, H-5), 4.24 (d, J = 13.2 Hz, 1H, H-1), 4.30 (dd, J = 14.0, 7.2 Hz, 1H, H-6), 6.63 (s, 1H, H-3), 7.00 (t, J = 7.6 Hz, 1H, Ar-H), 7.24 (t, J = 7.6 Hz, 3H, Ar-H), 7.35 (t, J = 7.2 Hz, 1H, Ar-H), 7.46 (dd, J = 15.2, 9.2 Hz, 6H, Ar-H), 7.67 (d, J = 7.6 Hz, 1H, Ar-H), 7.72 (d, J = 7.6 Hz, 2H, Ar-H), 10.26 (s, 1H, NH).13C NMR (100 MHz, DMSO): δ 34.6, 39.6, 58.6, 119.4, 123.7, 124.0, 126.8, 127.0, 127.9, 128.4, 128.9, 129.1, 129.3, 130.1, 131.0, 133.4, 137.6, 139.2, 139.6, 158.7, 167.4, 195.7.MS (EI, 70 eV) m/z (%): 401 (M+, 3), 347 (2), 283 (3), 265 (4), 236 (3), 219 (5), 197 (3), 179 (5), 160 (4), 132 (5), 108 (48), 81 (28), 52 (100). Anal. Calcdfor C25H20ClNO2: C, 74.71; H, 5.02; N, 3.49. Found: C, 74.75; H, 5.06; N, 3.55.

6-(4-methoxyphenyl)-2-oxo-N,4-diphenylcyclohex-3-enecarboxamide (4d)

White solid, yield: (96%); mp 217-219 ºC. IR (KBr) (νmax/cm-1): 3306, 3203, 1680, 1666, 1651, 1603, 1547, 1444, 1362, 1175, 759, 692. 1H NMR (400 MHz, CDCl3): 2.32 (s, 3H, OCH3), 3.06 (dd, J = 18.4, 7.6 Hz, 1H, H-5), 3.36 (dd, J = 18.4, 4.8 Hz, 1H, H'-5), 3.71 (d, J = 8.0 Hz, 1H, H-1), 4.17 (dd, J = 12.8, 7.6 Hz, 1H, H-6), 6.58 (s, 1H, H-3), 7.08 (t, J = 7.2 Hz, 1H, Ar-H), 7.12 (d, J = 8.0 Hz, 2H, Ar-H), 7.21 (d, J = 8.0 Hz, 2H, Ar-H), 7.28 (t, J = 8.4 Hz, 3H, Ar-H), 7.40-7.47 (m, 5H, Ar-H), 7.56(t, J = 6.4 Hz, 2H, Ar-H), 8.01 (s, 1H, NH).13C NMR (100 MHz, CDCl3): δ 21.0, 34.1, 40.9, 59.5, 124.2, 124.3, 126.3, 126.4, 127.2, 128.8, 128.9, 129.4, 129.4, 130.6, 136.7, 137.6, 137.8 139.2, 160.0, 165.4, 195.8;MS (EI, 70 eV) m/z (%): 397 (M+, 1), 392 (1), 381 (35), 344 (1), 289 (4), 261 (100), 228 (6), 202 (3), 171 (4), 145 (25), 115 (23), 93 (37), 65 (6). Anal. Calcdfor C25H20N2O4: C, 78.57; H, 5.83; N, 3.52. Found: C, 78.70; H, 5.94; N, 3.60.

6-(4-nitrophenyl)-2-oxo-N,4-diphenylcyclohex-3-enecarboxamide (4e)

Pale yellow solid, yield: (94%); mp 202-204 ºC. IR (KBr) (νmax/cm-1): 3415, 3304, 1663, 1606, 1555, 1517, 1445, 1349, 1176, 854, 759, 752, 692. 1H NMR (400 MHz, CDCl3): 3.05 (dd, J = 18.0, 8.4 Hz, 1H, H-5), 3.33 (dd, J = 18.0, 4.8 Hz, 1H, H'-5), 3.76 (d, J = 9.2 Hz, 1H, H-1), 4.27 (m, 1H, H-6), 6.58 (s, 1H, H-3), 7.09 (t, J = 7.2 Hz, 1H, Ar-H), 7.27 (t, J = 8.0 Hz, 2H, Ar-H), 7.39-7.48 (m, 5H, Ar-H), 7.49-7.55 (m, 4H, Ar-H), 8.16(d, J = 8.4 Hz, 2H, Ar-H), 8.32 (s, 1H, NH).13C NMR (100 MHz, CDCl3): δ 33.8, 41.3, 58.4, 120.0, 124.0, 124.2, 124.7, 126.3, 126.3, 128.4, 128.7, 128.9, 129.0, 131.0, 137.2, 137.3 146.9, 149.8, 159.5, 164.7, 194.7.MS (EI, 70 eV) m/z (%): 412 (M+, 44), 344 (7), 320 (7), 292 (82), 266 (14), 228 (4), 202 (12), 157 (30), 115 (27), 93 (100), 66 (19). Anal. Calcdfor C25H20N2O4: C, 72.80; H, 4.89; N, 6.79. Found: C, 72.87; H, 4.94; N, 6.85.

6-(2,6-dichlorophenyl)-2-oxo-N,4-diphenylcyclohex-3-enecarboxamide (4f)

White solid, yield: (95%); mp 188-190 ºC. IR (KBr) (νmax/cm-1): 3418, 3387, 1698, 1659, 1600, 1517, 1436, 1360, 1172, 768, 757, 691. 1H NMR (400 MHz, CDCl3): 2.98 (dd, J = 18.0, 4.8 Hz, 1H, H-5), 3.60 (ddd, J = 18.8, 12.0, 2.4 Hz, 1H, H'-5), 4.78 (d, J = 13.2 Hz, 1H, H-1), 5.01 (td, J = 12.4, 4.8 Hz, 1H, H-6), 6.64 (d, J = 2.4 Hz, 1H, H-3), 7.05 (t, J = 7.2 Hz, 1H, Ar-H), 7.15 (t, J = 8.0 Hz, 1H, Ar-H), 7.25 (t, J = 8.0 Hz, 2H, Ar-H), 7.30 (d, J = 8.0 Hz, 1H, Ar-H), 7.41 (dd, J = 8.0, 1.2 Hz, 1H, Ar-H), 7.44 (d, J = 3.2 Hz, 2H, Ar-H), 7.46-7.49 (m, 3H, Ar-H), 7.59-7.61 (m, 2H, Ar-H), 8.21 (s, 1H, NH).13C NMR (100 MHz, CDCl3): δ 30.4, 38.7, 55.6, 120.1, 124.2, 126.2, 128.8, 128.9, 129.3, 130.2, 130.7, 133.9, 135.9, 137.1, 137.5 137.6, 159.6, 165.5, 195.1.MS (EI, 70 eV) m/z (%): 436 (M+, 6), 435 (14), 400 (100), 372 (1), 343 (6), 316 (36), 281 (36), 256 (9), 226 (6), 199 (32), 157 (35), 115 (45), 93 (71), 65 (20). Anal. Calcdfor C25H19Cl2NO2: C, 68.82; H, 4.39; N, 3.21. Found: C, 68.88; H, 3.30; N, 6.85.

6-(4-cyanophenyl)-2-oxo-N,4-diphenylcyclohex-3-enecarboxamide (4g)

White solid, yield: (99%); mp 224-226 ºC. IR (KBr) (νmax/cm-1): 3308, 2230, 1672, 1656, 1603, 1543, 1443, 757, 692. 1H NMR (400 MHz, DMSO): 3.07 (dd, J = 18.0, 4.0 Hz, 1H, H-5), 3.18 (dd, J = 17.6, 10.4 Hz, 1H, H'-5), 3.95 (td, J = 13.2, 4.8 Hz, 1H, H-6), 4.02 (d, J = 13.2 Hz, 1H, H-1), 6.60 (d, J = 1.6 Hz, 1H, H-3), 7.01 (t, J = 7.2 Hz, 1H, Ar-H), 7.24 (d, J = 8.0 Hz, 2H, Ar-H), 7.44 (d, J = 8.8 Hz, 3H, Ar-H), 7.47 (d, J = 0.8 Hz, 2H, Ar-H), 7.66 (d, J = 8.0 Hz, 2H, Ar-H), 7.73 (t, J = 5.2 Hz, 2H, Ar-H), 7.80 (d, J = 8.0 Hz, 2H, Ar-H), 10.10 (s, 1H, NH).13C NMR (100 MHz, DMSO): δ 35.1, 43.4, 59.3, 110.2, 119.2, 119.5, 123.8, 123.9, 126.9, 129.1, 129.2, 129.3, 131.0, 132.8, 137.7 139.0, 148.3, 159.2, 167.4, 195.3.MS (EI, 70 eV) m/z (%): 392 (M+, 41), 344 (5), 300 (7), 272 (100), 243 (6), 196 (4), 157 (38), 115 (35), 93 (70), 65 (14). Anal. Calcdfor C26H20N2O2: C, 79.57; H, 5.14; N, 7.14. Found: C, 79.70; H, 5.22; N, 7.21.

6-(3-chlorophenyl)-2-oxo-N,4-diphenylcyclohex-3-enecarboxamide (4h)

White solid, yield: (95%); mp 187-189 ºC. IR (KBr) (νmax/cm-1): 3368, 3302, 3086, 1665, 1628, 1600, 1560, 1498, 1445, 1368, 1247, 758, 692. 1H NMR (400 MHz, DMSO): 3.06 (dd, J = 18.0, 4.4 Hz, 1H, H-5), 3.17 (m, 1H, H'-5), 3.86 (td, J = 12.8, 4.4 Hz, 1H, H-6), 3.97 (d, J = 13.2 Hz, 1H, H-1), 6.58 (d, J = 2.0 Hz, 1H, H-3), 7.01 (t, J = 7.2 Hz, 1H, Ar-H), 7.24 (d, J = 8.4 Hz, 2H, Ar-H), 7.27 (t, J = 2.0 Hz, 1H, Ar-H), 7.34 (t, J = 8.0 Hz, 1H, Ar-H), 7.40 (d, J = 8.0 Hz, 1H, Ar-H), 7.44-7.47 (m, 5H, Ar-H), 7.55 (s, 1H, Ar-H), 7.74 (dd, J = 7.2, 2.4 Hz, 2H, Ar-H), 10.08 (s, 1H, NH).13C NMR (100 MHz, DMSO): δ 35.5, 43.1, 59.7, 119.6, 123.8, 126.8, 126.9, 127.3, 128.0, 129.1, 129.3, 130.6, 130.9, 133.4, 137.8, 139.1, 145.1, 159.4, 167.6, 195.5.MS (EI, 70 eV) m/z (%): 401 (M+, 39), 342 (3), 309 (7), 281 (90), 252 (5), 228 (13), 202 (13), 179 (1), 157 (34), 115 (45), 93 (100), 65 (20). Anal. Calcdfor C25H20ClNO2: C, 74.71; H, 5.02; N, 3.49. Found: C, 74.78; H, 5.15; N, 3.62.

2-oxo-N,4-diphenyl-6-(pyridin-3-yl)cyclohex-3-enecarboxamide (4i)

White solid, yield: (92%); mp 195-197 ºC. IR (KBr) (νmax/cm-1): 3399, 3086, 1696, 1633, 1607, 1557, 1444, 1369, 1235, 1176, 756, 715, 693. 1H NMR (400 MHz, DMSO): 3.09 (dd, J = 18.2, 4.4 Hz, 1H, H-5), 3.21 (ddd, J = 18.0, 11.4, 2.0 Hz, 1H, H'-5), 3.88 (td, J = 13.0, 4.8 Hz, 1H, H-6), 3.51 (d, J = 12.8 Hz, 1H, H-1), 6.60 (d, J = 2.0 Hz, 1H, H-3), 7.01 (t, J = 7.2 Hz, 1H, Ar-H), 7.24 (t, J = 12.8 Hz, 2H, Ar-H), 7.35 (dd, J = 4.8, 7.6 Hz, 1H, Ar-H), 7.43 (d, J = 7.6 Hz, 2H, Ar-H), 7.47 (dd, J = 2.4, 5.2 Hz, 2H, Ar-H), 7.75 (dd, J = 7.4, 2.4 Hz, 2H, Ar-H), 7.89 (d, J = 8.0 Hz, 1H, Ar-H), 8.42 (dd, J = 4.8, 1.2 Hz, 1H, Ar-H), 8.65 (d, J = 1.6 Hz, 1H, Ar-H), 10.10 (s, 1H, NH).13C NMR (100 MHz, DMSO): δ 35.2, 41.1, 59.6, 119.5, 123.9, 126.9, 129.1, 129.3, 130.9, 135.5, 137.8, 137.9, 139.0, 148.6, 149.7, 159.4, 167.5, 195.4.MS (EI, 70 eV) m/z (%): 368 (M+, 43), 344 (1), 309 (2), 281 (39), 248 (100), 220 (14), 197 (3), 157 (21), 132 (28), 93 (96), 65 (13). Anal. Calcdfor C24H20N2O2: C, 78.24; H, 5.47; N, 7.60. Found: C, 78.31; H, 5.58; N, 7.69.

2-oxo-N,4-diphenyl-6-(pyridin-4-yl)cyclohex-3-enecarboxamide (4j)

White solid, yield: (97%); mp 202-204 ºC. IR (KBr) (νmax/cm-1): 3467, 3267, 3073, 1695, 1647, 1603, 1555, 1497, 1444, 1366, 1177, 756, 692. 1H NMR (400 MHz, DMSO): 3.08 (dd, J = 18.0, 4.8 Hz, 1H, H-5), 3.17 (dd, J = 17.6, 11.4, Hz, 1H, H'-5), 3.87 (td, J = 13.2, 4.8 Hz, 1H, H-6), 4.01 (d, J = 13.2 Hz, 1H, H-1), 6.60 (d, J = 1.6 Hz, 1H, H-3), 7.01 (t, J = 7.2 Hz, 1H, Ar-H), 7.25 (t, J = 8.0 Hz, 2H, Ar-H), 7.45 (t, J = 7.6 Hz, 7H, Ar-H), 7.74 (t, J = 5.6 Hz, 2H, Ar-H), 8.51 (d, J = 6.0 Hz, 2H, Ar-H), 10.13 (s, 1H, NH).13C NMR (100 MHz, DMSO): δ 34.8, 42.7, 59.0, 119.5, 123.4, 123.8, 123.9, 126.9, 129.1, 129.3, 131.0, 137.7, 139.0, 150.1, 151.3, 159.2, 167.4, 195.2.MS (EI, 70 eV) m/z (%): 368 (M+, 30), 344 (1), 309 (2), 281 (29), 248 (19), 220 (10), 197 (3), 171 (15), 144 (34), 115 (55), 93 (100), 65 (25). Anal. Calcdfor C24H20N2O2: C, 78.24; H, 5.47; N, 7.60. Found: C, 78.31; H, 5.58; N, 7.69.

6-(2,3-dimethoxyphenyl)-2-oxo-N,4-diphenylcyclohex-3-enecarboxamide (4k)

White solid, yield: (90%); mp 196-198 ºC. IR (KBr) (νmax/cm-1): 3413, 1666, 1600, 1556, 1477, 1445, 1365, 1274, 1073, 1002, 756, 693. 1H NMR (400 MHz, CDCl3): 3.01 (d, J = 17.6 Hz, 1H, H-5), 3.44 (ddd, J = 17.5, 10.0, 3.2 Hz, 1H, H'-5), 3.88 (s, 3H, OCH3), 4.06 (s, 3H, OCH3), 4.49 (d, J = 8.8 Hz, 2H, H-1 and H-6), 6.53 (d, J = 2.8 Hz, 1H, H-3), 6.79 (dd, J = 1.2, 8.0 Hz, 1H, Ar-H), 6.96 (t, J = 8.0 Hz, 1H, Ar-H), 7.08 (t, J = 7.2 Hz, 1H, Ar-H), 7.22 (dd, J = 1.2, 8.0 Hz, 1H, Ar-H), 7.32 (t, J = 8.4 Hz, 3H, Ar-H), 7.39 (d, J = 7.2 Hz, 2H, Ar-H), 7.51-7.55 (m, 4H, Ar-H), 8.24 (s, 1H, NH).13C NMR (100 MHz, CDCl3): δ 28.6, 36.0, 55.6, 58.2, 60.8, 111.3, 119.8, 120.3, 121.6, 123.9, 124.8, 125.1, 126.4, 127.7, 128.9, 130.5, 135.7, 137.7, 146.7, 152.9, 160.1, 165.5, 196.0.MS (EI, 70 eV) m/z (%): 354 (M+-1, 2), 368 (3), 344 (1), 299 (7), 265 (1), 241 (100), 198 (26), 172 (1), 150 (74), 115 (15), 91 (7), 57 (9). Anal. Calcdfor C27H25NO4: C, 75.86; H, 5.89; N, 3.28. Found: C, 75.95; H, 5.94; N, 3.40.

2. NMR (1H and 13C) and Mass spectra of highly functionalized cyclohexenones4a-k:

Figure 1.1H NMR spectra of compound 4a

Figure 2.13C NMR spectra of compound 4a

Figure 3. Mass spectra of compound 4a

Figure 4.1H NMR spectra of compound 4b

Figure 5.13C NMR spectra of compound 4b

Figure 6. Mass spectra of compound 4b

Figure 7.1H NMR spectra of compound 4c

Figure 8.13C NMR spectra of compound 4c

Figure 9. Mass spectra of compound 4c

Figure 10.1H NMR spectra of compound 4d

Figure 11.13C NMR spectra of compound 4d

Figure 12. Mass spectra of compound 4d

Figure 13.1H NMR spectra of compound 4e

Figure 14.13C NMR spectra of compound 4e

Figure 15. Mass spectra of compound 4e

Figure 16.1H NMR spectra of compound 4f

Figure 17.13C NMR spectra of compound 4f

Figure 18. Mass spectra of compound 4f

Figure 19.1H NMR spectra of compound 4g

Figure 20.13C NMR spectra of compound 4g

Figure 21. Mass spectra of compound 4g

Figure 22.1H NMR spectra of compound 4h

Figure 23.13C NMR spectra of compound 4h

Figure 24. Mass spectra of compound 4h

Figure 25.1H NMR spectra of compound 4i

Figure 26.13C NMR spectra of compound 4i

Figure 27. Mass spectra of compound 4i

Figure 28.1H NMR spectra of compound 4j

Figure 29.13C NMR spectra of compound 4j

Figure 30. Mass spectra of compound 4j

Figure 31.1H NMR spectra of compound 4k

Figure 32.13C NMR spectra of compound 4k

Figure 33. Mass spectra of compound 4k

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