Retro-ene type fragmentation of allylic dithiolcarbonates

Tetrahedron Letters

Volumn 37, Issue 14, 1996, Pages 2445-2448

  Eto, Masashi ^a   Nishimoto, Mitsuhiro ^a   Kubota, Shoji ^a   Matsuoka, Toshikazu ^a   Harano, Kazunobu ^a  

^a KUMAMOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

SULFIDE;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0029945595     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00314-0     Document Type: Article

References (15)

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2. K. Harano and T. Taguchi, Chem. Pharm. Bull., 1972, 20, 2348, 2357: 1975, 23, 467.
3. K. Harano, H. Kiyonaga and T. Hisano, Tetrahedron Lett., 1991, 32, 7557.
4. (a) K. Harano, N. Ohizumi and T. Hisano, Tetrahedron Lett., 1985, 26, 4203.
5. (b) K. Harano, N. Ohizumi, K. Misaka, S. Yamashiro and T. Hisano, Chem. Pharm. Bull., 1990, 38, 619.
6. (a) K. Harano, S. Yamashiro, K. Misaka and T. Hisano, Chem. Pharm. Bull., 1990, 38, 2956.
7. (b) K. Harano, K. Miyoshi and T. Hisano, Chem. Pharm. Bull., 1990, 33, 1861.
8. Heating of a 1:1 inclusion compound (ß-CyD-2a) at 120 °C for 6h, followed by treatment with aq. DMSO and extraction with benzene gave pure E-(3-phenylallyl) methyl sulfide (E-3a) in 81 % yield. The S-acetylmethyl derivative smoothly extruded COS to give the corresponding sulfide in 90% yield. The methyl substituent on 2-position of the allylic moiety retarded the reaction rate.
9. 2 (0.1 eq) is 13.5 kcal/mol. (formula presented)
10. J. J. P. Stewart, QCPE Bull., 1989, 9, 10: idem, J. Comp. Chem., 1989, 10, 209, 221.
11. J. J. P. Stewart, QCPE Bull., 1989, 9, 10: idem, J. Comp. Chem., 1989, 10, 209, 221.
12. Steric effect may be operative. Inspection of the optimized structures indicates that the OC - SCHRCH= bond of the secondary ones is elongated as compared with the primary ones.
13. Gaussian 92/DFT, Revision G.1, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G.Johnson, M. W. Wong, J. B. Foresman, M. A. Robb, M. Head-Gordon, E. S. Replogle, R. Gomperts, J. L. Andres, K. Raghavachari, J. S. Binkley, C. Gonzalez, R. L. Martin, D. J. Fox, D. J. Defrees, J. Baker, J. J. P. Stewart, and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1993. (formula presented)
14. K. N. Houk, Y. Li and J. D. Evanseck, Angew. Chem. Int. Ed. Engl., 1992,31 ,682.
15. The MO simulations on proton-coordinated reaction for 2A implied a different mechanism, i.e., [3,3]-sigmatropic rearrangement. The 6-31G* simulation predicts that fragmentation of COS does not occur and betaine-type intermediate is produced.