6
052
Acknowledgements
This work was supported by Glaxo Wellcome through a fellowship to L.G. The authors thank
Alain Valleix for mass spectroscopy analysis.
References
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1
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969, 34, 2163±2169. (e) Benazza, T.; Uzan, R.; Beaupere, D.; Demailly, G. Tetrahedron Lett. 1992, 33, 4901±
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Á
8. (a) Viehe, H. G.; Janousek, Z. Angew. Chem. 1971, 83, 614±615. (b) Benazza, T.; Uzan, R.; Beaupere, D.;
Á
Demailly, G. Tetrahedron Lett. 1992, 33, 3129±3132.
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1
0. (a) Mattes, H.; Benezra, C. Tetrahedron Lett. 1987, 28, 1697±1698. (b) Sonnet, P. E. Synth. Commun. 1976, 6, 21±
6. (c) Wagner, A.; Heitz, M. P.; Mioskowski, C. Tetrahedron Lett. 1989, 30, 557±558. (d) Schlama, T.;
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2
1
1. (a) Original conditions for the preparation of 1: Copeland, C.; Stick, R. V. Aust. J. Chem. 1984, 37, 1483±1487. (b)
New method for the preparation of CPMA: To dimethylthiocarbamoyl chloride (1 g, 8.1 mmol) in
dichloromethane (20 mL) under nitrogen was added thiophenol (0.67 mL, 6.5 mmol), triethylamine (1.1 mL, 8.1
mmol) and 4-dimethylaminopyridine (10 mg, 0.08 mmol). The mixture was heating at re¯ux for 12 h. Basic work-
2 2 3
up (CH Cl /NaHCO aq.) gave an oil and subsequent ¯ash chromatography (hexane:AcOEt, 3:1) gave the
corresponding dithiocarbamate (1.42 g, 89%). Treatment with phosgene (3.3 mL, 1.93 M in toluene) in toluene
ꢀ
(
10 mL) for 2 h at 60 C followed by concentration gave CPMA as a white solid which was washed with toluene.
) ꢀ (ppm) 4.07 (s, 6H), 7.37±7.66 (m, 3H), 7.79±7.82 (m, 2H). 13C NMR (50 MHz,
1
H NMR (300 MHz, CDCl
CDCl ) ꢀ (ppm) 178.7, 136.9, 133.6, 131.2, 124.7, 50.0, 47.8. IR (®lm CsI) ꢁ (cm ) 1667, 1596, 1476, 1441, 1406,
3
^
1
3
1
3
365, 1259, 1235, 1103, 1088, 990, 752, 688. Elemental analysis calcd for (C
0.0%; S, 13.6%. Found: C, 45.6%; H, 5.0%; Cl, 29.7%; S, 13.4%. Mp decomposes above 60 C.
9
H
11Cl
2
NS): C, 45.8%; H, 4.7%; Cl,
ꢀ
1
2. Munyemana, F.; Frisque-Hesbain, A.-M.; Devos, A.; Ghosez, L. Tetrahedron Lett. 1989, 30, 3077±3080.