Helvetica Chimica Acta Vol. 88 (2005)
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overnight at 208. H2O was added, and the aq. phase was extracted with CH2Cl2. The org. phase was dried
(MgSO4) and evaporated and the crude material purified by CC (SiO2, AcOEt/cyclohexane 7:3): (À)-5b
(60%). M.p. 68 728 (Et2O). [a]2D0 À15.33 (c 1.0, CHCl3). IR: 3426, 2953, 2880, 1465, 1370, 1306, 1274, 1207,
1166, 1132, 1072, 1004, 987, 792, 773, 726, 685, 555, 536, 453. 1H-NMR: 1.12 (d, J 8, 6 H); 1.34 (s, 1 H); 1.41
1.36 (m, 1 H); 1.62 1.55 (m, 1 H); 1.78 1.68 (m, 2 H); 1.84 (d, J 4.5, 1 H); 2.25 (dd, J 8.5, 1.5, 1 H); 2.46 (d,
J 1, 1 H); 2.66 (s, 3H); 3.19 ( AB(−d×), J 12.5, 1 H); 3.37 (AB(−d×), J 13, 1 H). 13C-NMR: 23.5 (q); 24.0 (t);
26.6 (q); 31.9 (t); 32.8 (q); 40.7 (t); 43.1 (s); 48.1 (s); 49.7 (d); 52.4 (t); 78.9 (d). ESI-MS: 230 ([M H] ), 252
([M Na] ). HR-ESI-MS: 230.1185 (C11H20NO2S , [M H] ; calc. 230.1215).
(2R)-N-Acryloylfenchane-8,2-sultam (1-[(3aS,6S,7aR)-1,4,5,6,7,7a-Hexahydro-7,7-dimethyl-2,2-dioxido-
3H-3a,6-methano-2,1-benzothiazol-1-yl]prop-2-en-1-one (À)-5c). As described for (À)-5e: (À)-5c (32%).
M.p. 107 1128 (AcOEt/hexane). [a]2D0 À57.8 (c 1.0, CHCl3). IR: 3431, 2971, 2878, 1675, 1619, 1469, 1411,
1338, 1313, 1286, 1269, 1253, 1174, 1147, 1035, 974, 799, 774, 544, 523. 1H-NMR: 0.91 (s, 3H); 1.27 ( s, 3 H); 1.33
(d, J 10.5, 1 H); 1.42 (m, 1 H); 1.63( m, 1 H); 1.77 (dt, J 11.5, 4, 1 H); 1.86 (m, 1 H); 1.89 (m, 1 H); 2.42 (d,
J 10.5, 1 H); 3.43 (AB(−d×), J 14, 1 H); 3.49 (AB(−d×), J 14, 1 H); 3.65 (s, 1 H); 5.85 (d, J 12, 1 H); 6.48 (d,
J 16, 1 H); 6.78 (dd, J 12, 16, 1 H). 13C-NMR: 22.7 (q); 23.7 (t); 25.1 (q); 32.1 (t); 39.4 (t); 44.9 (s); 46.3( s);
49.0 (d); 54.7 (t); 73.8 (d); 128.7 (d); 130.3 (t); 165.4 (s). ESI-MS: 292 ([M Na] ). HR-ESI-MS: 292.0982
(C13H19NNaO3S , [M Na] ; calc. 292.0983).
(2R)-N-Crotonoylfenchane-8,2-sultam ((2E)-1-[3aS,6S,7aR)-1,4,5,6,7,7a-Hexahydro-7,7-dimethyl-2,2-di-
oxido-3H-3a,6-methano-2,1-benzothiazol-1-yl]but-2-en-1-one; (À)-5d). As described for (À)-5e: (À)-5d (63%).
M.p. 154 1588 (hexane/AcOEt). [a]2D0 À42.25 (c 1.0, CHCl3). IR: 3435, 2979, 2878, 1674, 1633, 1443, 1333,
1289, 1230, 1172, 1147, 1086, 1023, 967, 806, 774, 644, 545, 521. 1H-NMR: 0.90 (s, 3 H); 1.26 (s, 3 H); 1.32 (d, J
10.5, 1 H); 1.41 (m, 1 H); 1.61 (m, 1 H); 1.76 (dt, J 12.5, 4, 1 H); 1.86 (m, 2 H); 1.94 (dd, J 5, 1.5, 2 H); 2.42
(m, 1 H); 3 .40 (AB(−d×), J 12.5, 1 H); 3.47 (AB(−d×), J 12.5, 1 H); 3.63 (d, J 1, 1 H); 6.48 (d, J 14, 1 H);
7.04 (dq, J 14, 5, 1 H). 13C-NMR: 18.3( q); 22.8 (q); 23.7 (t); 25.1 (q); 32.0 (t); 39.4 (t); 44.9 (s); 46.2 (s); 49.0
(d); 54.7 (t); 73.7 (d); 123.3 (d); 145.1 (d); 165.5 (s). ESI-MS: 306 ([M Na] ); 589 ([2M Na] ). HR-ESI-
MS: 306.1131 (C14H21NO3NaS , [M Na] ; calc. 306.1140).
(2R,2'R)-N,N'-Fumaroylbis[fenchane-8,2-sultam] ((2E)-1,4-Bis[3aS,6S,7aR)-1,4,5,6,7,7a-Hexahydro-7,7-
dimethyl-2,2-dioxido-3H-3a,6-methano-2,1-benzothiazol-1-yl]but-2-ene-1,4-dione; (À)-5e). A soln. of ()-5a
(100 mg, 0.46 mmol) in toluene (2 ml) was added dropwise at 08 to a 60% suspension of NaH in mineral oil
(46 mg, 1.15 mmol) in toluene (2 ml). After 30 min, but-2-enedioyl dichloride (85 ml, 0.29 mmol) was added
dropwise. The resulting mixture was stirred overnight at 208. Workup as described for (À)-5b and CC (SiO2,
AcOEt/hexane 9 :1 ! 6 :4) afforded (À)-5e (63%). Rf (toluene/AcOEt 7:3) 0.67. M.p. 208 2118 (MeOH/
AcOEt). [a]2D0 À93.01 (c 1, CHCl3). IR: 3430, 2957, 2877, 1671, 1470, 1324, 1213, 1169, 1149, 1087, 1045, 1023,
955, 771, 648, 546, 521. 1H-NMR: 0.91 (s, 6 H); 1.27 (s, 6 H); 1.33 (d, J 10, 4 H); 1.59 À 1.66 (m, 2 H); 1.75 1.81
(m, 2 H); 1.84 1.90 (m, 4 H); 2.43( d, J 9.5, 2 H); 3.42 (AB(−d×), J 13, 2 H); 3.49 (AB(−d×), J 12.5, 2 H);
3.63 (s, 2 H); 7.52 (s, 2 H). 13C-NMR: 22.8 (q); 23.7 (t); 25.0 (q); 32.1 (t); 39.4 (t); 45.0 (s); 46.4 (s); 48.9 (d); 54.6
(t); 73.9 (d); 132.6 (d); 163.6 (s). ESI-MS: 533 ([M Na] ), 1042 ([2M Na] ). HR-ESI-MS: 533.1754
(C24H34N2O6NaS2 , [M Na] ; calc. 533.1756).
[(2S,3S)-Bicyclo[2.2.1]hept-5-ene-2,3-diyl]bis[[3aS,6S,7aR)-1,4,5,6,7,7a-hexahydro-7,7-dimethyl-2,2-dioxi-
do-3H-3a,6-methano-2,1-benzothiazol-1-yl]methanone] (()-(2S,3S)-6). To a soln. of (À)-5e (51 mg, 0.1 mmol)
in CH2Cl2 (2 ml), 1m TiCl4 in CH2Cl2 (100 ml, 0.1 mmol) was added. Then, the mixture was cooled to À 788, and
cyclopenta-1,3-diene (83 ml, 1.0 mmol) was added slowly along the wall of the flask. After 24 h at À 788, the
mixture was quenched with NH4Fand equilibrated to 208. After addition of H2O, the mixture was extracted with
CH2Cl2. The org. phase was dried (MgSO4), and evaporated. Both conversion and d.e. were measured by
integration of the olef. protons in the 1H-NMR of the crude material. Pure material was obtained after
purification by CC (SiO2, from toluene to toluene/AcOEt 95 :5): ()-(2S,3S)-6. Oil. Rf (toluene/AcOEt 7:3)
0.74. [a]2D0 18.15 (c 1, CHCl3). IR: 3442, 2953, 2876, 1681, 1472, 1333, 1280, 1223, 1169, 1146, 1087, 1046,
1021, 820, 757, 619, 539, 518. 1H-NMR: 0.84 (s, 3H); 0.90 ( s, 3H); 1.23( s, 3H); 1.29 ( s, 3 H); 1.35 1.39 (m, 3 H);
1.54 1.62 (m, 4 H); 1.70 1.76 (m, 2 H); 1.81 1.87 (m, 4 H); 2.08 (d, J 8.5, 1 H); 2.30 (dd, J 2.0, 8.5, 2 H);
2.99 (dd, J 1.5, 1.0, 1 H); 3.20 (d, J 1.5, 1 H); 3.41 3.48 (m, 5 H); 3.53 (s, 1 H); 3.58 (s, 1 H); 3 .81 (dd, J 3.0,
2.0, 1 H); 6.10 (dd, J 3.0, 2.5, 1 H); 6.45 (dd, J 3.5, 2.5, 1 H). 13C-NMR: 22.7 (2 C); 23.7; 25.0; 32.1; 32.2; 39.3;
44.9 (2 C); 46.05(2 C); 46.8; 47.3; 49.1; 50.5 (2 C); 52.4; 54.7; 74.2; 74.3; 134.8; 137.8; 173.8; 174.3. ESI-MS: 599
([M Na] ), 1175 ([2M Na] ). HR-ESI-MS: 599.2220 (C29H40N2O6NaS2 , [M Na] ; calc. 599.2226).
[(2R,3R)-Bicyclo[2.2.1]hept-5-ene-2,3-diyl]bis[(3aS,6S,7aR)-1,4,5,6,7,7a-hexahydro-7,7-dimethyl-2,2-diox-
ido-3H-3a,6-methano-2,1-benzothiazol-1-yl]methanone] ((À)-(2R,3R)-6). Cyclopenta-1,3-diene (83 ml,
1 mmol) was added to a soln. of (À)-5e (51 mg, 0.1 mmol) in the desired solvent (2 ml; see Table 2) at À 788