Helvetica Chimica Acta – Vol. 94 (2011)
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2 H); 3.99 (t, J ¼ 6.8, 1 H); 7.12 (d, J ¼ 15.4, 1 H); 7.16 – 7.24 (m, 2 H); 7.46 – 7.50 (m, 2 H); 7.77 (d, J ¼ 15.4,
1 H). ESI-MS: 382.1 ([M þ Na]þ). HR-ESI-MS: 382.1453 (C20H25NNaO3Sþ; calc. 382.1450).
(ꢀ)-(2R)-N-[4-(Methylthio)cinnamoyl]bornane-10,2-sultam (¼(ꢀ)-(2E)-3-[4-(Methylthio)phenyl]-
1-[(3aS,6R,7aR)-tetrahydro-8,8-dimethyl-2,2-dioxido-3H-3a,6-methano-2,1-benzisothiazol-1(4H)-yl]-
prop-2-en-1-one; 2e): Yield 87%. M.p. 153 – 1588. [a]2D0 ¼ ꢀ86.6 (c ¼ 1.0, CHCl3). IR: 3006, 2986, 2963,
2940, 2878, 1671, 1614, 1589, 1550, 1494, 1456, 1407, 1368, 1336, 1315, 1275, 1230, 1206, 1187, 1164, 1132,
1112, 1093, 1062, 1042, 988, 882, 815, 762, 615, 546, 537, 500, 480, 463, 404. 1H-NMR: 0.99 (s, 3 H); 1.20 (s,
3 H); 1.38 – 1.50 (m, 2 H); 1.85 – 1.95 (m, 3 H); 2.13 – 2.18 (m, 2 H); 2.50 (s, 3 H); 3.47, 3.56 (AB, J ¼ 14,
2 H); 3.99 (t, J ¼ 5,4, 1 H); 7.11 (d, J ¼ 15.4, 1 H); 7.18 – 7.27 (m, 2 H); 7.47 – 7.51 (m, 2 H); 7.74 (d, J ¼ 15.4,
1 H). ESI-MS: 414,1 ([M þ Na]þ). HR-ESI-MS: 414.1174 (C11H16NaOþ3 ; calc. 414.1187).
(ꢀ)-(2R)-N-(4-Fluorocinnamoyl)bornane-10,2-sultam (¼(ꢀ)-(2E)-3-(4-Fluorophenyl)-1-[(3aS,
6R,7aR)-tetrahydro-8,8-dimethyl-2,2-dioxido-3H-3a,6-methano-2,1-benzisothiazol-1(4H)-yl]prop-2-en-
1-one; 2f): Yield 89%. M.p. 178 – 1868. [a]2D0 ¼ ꢀ90.2 (c ¼ 1.0, CHCl3). IR: 3008, 2993, 2946, 2904, 1678,
1626, 1598, 1509, 1459, 1416, 1394, 1366, 1332, 1283, 1265, 1232, 1206, 1159, 1130, 1112, 1063, 1042, 987,
940, 883, 830, 777, 548, 526, 499, 455, 439. 1H-NMR: 0.99 (s, 3 H); 1.21 (s, 3 H); 1.39 – 1.50 (m, 2 H); 1.91 –
1.96 (m, 3 H); 2.14 – 2.18 (m, 2 H); 3.46, 3.57 (AB, J ¼ 14, 2 H); 4.0 (t, J ¼ 7.2, 1 H); 7.07 (d, J ¼ 15.4, 1 H);
7.03 – 7.13 (m, 2 H); 7.54 – 7.61 (m, 2 H); 7.75 (d, J ¼ 15.4, 1 H). ESI-MS: 386.1 ([M þ Na]þ). HR-ESI-
MS: 386.1202 (C19H22FNNaO3Sþ; calc. 386.1216).
(ꢀ)-(2R)-N-(4-Chlorocinnamoyl)bornane-10,2-sultam (¼(ꢀ)-(2E)-3-(4-Chlorophenyl)-1-[(3aS,
6R,7aR)-tetrahydro-8,8-dimethyl-2,2-dioxido-3H-3a,6-methano-2,1-benzisothiazol-1(4H)-yl]prop-2-en-
1-one; 2g): Yield 79%. M.p. 207 – 2128. [a]2D0 ¼ ꢀ98.8 (c ¼ 1.0, CHCl3). IR: 3007, 2991, 2941, 2880, 1676,
1628, 1593, 1494, 1410, 1373, 1343, 1325, 1311, 1296, 1281, 1236, 1219, 1165, 1132, 1116, 1092, 1064, 1013,
992, 885, 829, 819, 782, 762, 730, 547, 536, 499, 491, 405. 1H-NMR: 0.99 (s, 3 H); 1.20 (s, 3 H); 1.34 – 1.51
(m, 2 H); 1.85 – 1.98 (m, 3 H); 2.14 – 2.18 (m, 2 H); 3.47, 3.54 (AB, J ¼ 13.8, 2 H); 3.99 (t, J ¼ 6.8, 1 H);
7.14 (d, J ¼ 15.5, 1 H); 7.10 – 7.37 (m, 2 H); 7.49 – 7.54 (m, 2 H); 7.73 (d, J ¼ 15.5, 1 H). ESI-MS: 402.1
([M þ Na]þ). HR-ESI-MS: 402.0907 (C19H22ClNNaO3Sþ; calc. 402.0924).
(ꢀ)-(2R)-N-(4-Bromocinnamoyl)bornane-10,2-sultam (¼(ꢀ)-(2E)-3-(4-Bromophenyl)-1-[(3aS,
6R,7aR)-tetrahydro-8,8-dimethyl-2,2-dioxido-3H-3a,6-methano-2,1-benzisothiazol-1(4H)-yl]prop-2-en-
1-one; 2h): Yield 76%. M.p. 208 – 2108. [a]2D0 ¼ ꢀ79.8 (c ¼ 1.0, CHCl3). IR: 3006, 2989, 2939, 2879, 1676,
1628, 1587, 1565, 1490, 1459, 1417, 1405, 1392, 1374, 1343, 1325, 1296, 1275, 1236, 1219, 1165, 1132, 1115,
1064, 1039, 1009, 991, 884, 826, 817, 781, 760, 727, 546, 535, 497, 445. 1H-NMR: 0.99 (s, 3 H); 1.20 (s, 3 H);
1.38 – 1.51 (m, 2 H); 1.92 – 1.98 (m, 3 H); 2.14 – 2.18 (m, 2 H); 3.47, 3.57 (AB, J ¼ 13.7, 2 H); 3.99 (t, J ¼ 5.8,
1 H); 7.15 (d, J ¼ 15.4, 1 H); 7.11 – 7.50 (m, 4 H); 7.71 (d, J ¼ 15.4). ESI-MS: 446.0 ([M þ Na]þ). HR-ESI-
MS: 446.0412 (C19H19BrN4NaO3Sþ; calc. 446.0424).
(ꢀ)-(2R)-N-[4-(Trifluoromethoxy)cinnamoyl]bornane-10,2-sultam (¼(ꢀ)-(2E)-1-[(3aS,6R,7aR)-
Tetrahydro-8,8-dimethyl-2,2-dioxido-3H-3a,6-methano-2,1-benzisothiazol-1(4H)-yl]-3-[4-(trifluorome-
thoxy)phenyl]prop-2-en-1-one; 2i): Yield 91%. M.p. 120 – 1258. [a]2D0 ¼ ꢀ81.3 (c ¼ 1.0, CHCl3). IR: 3000,
2963, 2883, 1682, 1634, 1508, 1457, 1418, 1408, 1374, 1337, 1288, 1272, 1259, 1214, 1147, 1135, 1112, 1069,
995, 982, 880, 833, 796, 776, 757, 546, 536, 498. 1H-NMR: 0.99 (s, 3 H); 1.20 (s, 3 H); 1.39 – 1.51 (m, 2 H);
1.91 – 1.96 (m, 3 H); 2.14 – 2.19 (m, 2 H); 3.48, 3.57 (AB, J ¼ 13.8, 2 H); 4.00 (t, J ¼ 5.6, 1 H); 7.14 (d, J ¼
15.5, 1 H); 7.10 – 7.27 (m, 2 H); 7.58 – 7.64 (m, 2 H); 7.75 (d, J ¼ 15.5, 1 H). ESI-MS: 452.1 ([M þ Na]þ).
HR-ESI-MS: 452.1119 (C20H22F3NNaO4Sþ; calc. 452.1139).
(ꢀ)-(2R)-N-[4-(Trifluoromethyl)cinnamoyl]bornane-10,2-sultam (¼(ꢀ)-(2E)-1-[(3aS,6R,7aR)-
Tetrahydro-8,8-dimethyl-2,2-dioxido-3H-3a,6-methano-2,1-benzisothiazol-1(4H)-yl]-3-[4-(trifluorome-
thyl)phenyl]prop-2-en-1-one; 2j): Yield 75%. M.p. 164 – 1688. [a]2D0 ¼ ꢀ76.5 (c ¼ 0.26, CHCl3). IR: 2992,
2966, 2939, 2904, 1683, 1632, 1418, 1335, 1321, 1285, 1233, 1214, 1169, 1127, 1113, 1070, 1060, 1045, 1015,
987, 883, 833, 769, 545, 486, 457. 1H-NMR: 1.00 (s, 3 H); 1.21 (s, 3 H); 1.34 – 1.60 (m, 2 H); 1.93 – 2.05 (m,
3 H); 2.15 – 2.19 (m, 2 H); 3.48, 3.58 (AB, J ¼ 13.9, 2 H); 4.00 (t, J ¼ 7, 1 H); 7.23 (d, J ¼ 15.4, 1 H); 7.28 –
7.71 ( m, 4 H); 7.78 (d, J ¼ 15.4, 1 H). ESI-MS: 436.1 ([M þ Na]þ). HR-ESI-MS: 436.1170
(C20H22F3NNaO3Sþ; calc. 436.1129).
3. EtMgBr Addition to 2: General Procedure B. A soln. of substrate 2a – 2m (1 mmol) in anh. THF
(5 ml) under Ar was cooled to ꢀ 788. Then alkylmagnesium halide (1m or 2m soln. in THF, 2.2 equiv.) was