Oxidative fragmentations of selected 1-alkenyl sulfoxides. Chemical and spectroscopic evidence for 1-alkenesulfinyl chlorides

Tetrahedron Letters

Volumn 37, Issue 14, 1996, Pages 2345-2348

  Schwan, Adrian L ^a   Kalin, Mark L ^a   Vajda, Kristin E ^a   Xiang, Ting Jian ^a   Brillon, Denis ^a  

^a UNIVERSITY OF GUELPH   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

SULFINIC ACID DERIVATIVE;

ARTICLE; DRUG STRUCTURE; DRUG SYNTHESIS; INFRARED SPECTROPHOTOMETRY; REACTION ANALYSIS;

EID: 0029989539     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00281-X     Document Type: Article

References (24)

1. Tillett, J.G., in The Chemistry of Sulfinic Acids, Esters and their Derivatives, Patai, S. ed., John Wiley & Sons, New York, 1990. Chapter 19.
2. Walker, A.J. Tetrahedron: Asymmetry 1992, 3, 961-968.
3. Andersen, K.K.; Gaffield, W.; Papanikolaou, N.E.; Foley, J.W.; Perkins, R.I. J. Am. Chem. Soc. 1964, 86, 5637-5646.
4. Many other research groups have contributed to this area. See for examples: a) Evans, D.A.; Faul, M.M.; Colombo, L.; Bisaha, J.J.; Clardy, J.; Cherry, D. J. Am. Chem. Soc. 1992, 114, 5977-5985.
5. b) Fernández, I.; Khiar, N.; Liera, J.M.; Alcudia, F.; J. Org. Chem. 1992, 57, 6789-6796.
6. a) Kee, M.-L.; Douglass, I.B. Org. Prep. Proc. 1970, 2, 235-244 and references therein,
7. b) Youn, J.-H.; Herrmann, R. Tetrahedron Lett. 1986, 27, 1493-1494.
8. c) Youn, J.-H.; Hermann, R. Synthesis 1987, 72-73.
9. d) Thea, S.; Cevasco, G. Tetrahedron Lett. 1987, 28, 5193-5194.
10. Schwan, A.L.; Dufault, R. Tetrahedron Lett. 1992, 33, 3973-3974.
11. For another general sulfinyl chloride preparation that begins with a sulfoxide: Uchino, M.; Suzuki, K.; Sekiya, M., Chem. Pharm. Bull. 1979, 27, 1199-1206.
12. Schwan, A. L.; Brillon, D.; Dufault, R. Can. J. Chem. 1994, 72, 325-333.
13. 13C NMR, IR and MS were obtained.
14. In our experience, both sulfinyl chlorides and carboxylic acid chlorides move slightly on a TLC plate before hydroysis by the -OH groups of the silica gel and/or attachment to the -OH groups bring the movement of the substrate to a halt.
15. Craig, D.; Daniels, K.; MacKenzie, A.R. Tetrahedron 1993, 49, 11263-11304.
16. Sharma, N.K.; de Reinach-Hirtzbach, F.; Durst, T. Can. J. Chem. 1976, 54, 3012-3025.
17. Greene, T.W; Wuts, P.G.M. Protective Groups in Organic Synthesis, 2nd ed. Wiley-Interscience, New York, 1991; pp. 285-286.
18. a) Kawamoto, I.; Endo, R.; Ishikawa, K.; Kojima, K.; Miyauchi, M.; Nakayama, E. Synlett 1995, 575-577.
19. b) See also ref. 13, pp. 281-282.
20. Sulfoxides 7a-c, g and 8a-c, g were prepared by reacting the appropriate alkenesulfenate (see ref. 16) with diphenylmethyl bromide and P-methoxybenzyl bromide (49-75%). Compounds 7d-e and 8d-e were prepared from the reaction of the phenyl substituted ethenesulfenates derived from phenylthiirane ,S-oxide (ref. 16) with the appropriate aforementioned bromides. One reaction produced 7d (35%) and 7e (12%) while a second reaction afforded 8d (43%) and 8e (24%). Sulfoxide 8f was prepared by base catalyzed addition of p-methoxybenzyl mercaptan across phenylacetylene (cat. KOH, DMF, r.t.) followed by MCPBA oxidation (65% overall).
21. Refvik, M.D.; Froese, R.D.J.; Goddard, J.D.; Pham, H.H.; Pippert, M.F.; Schwan, A.L. J. Am. Chem. Soc. 1995, 117, 184-192.
22. Vacuum distillation was attempted for sulfinyl chlorides 9a and 9b (from 7a and 7b), but decomposition occurred upon concentration and mild heating of the samples.
23. The mixtures initially contain DPMCl or PMBCl as by-products. During and sometimes before chromatography, these chlorides undergo partial hydrolysis to their corresponding alcohols. Since the chlorides are less polar than the alkenesulfinates and the alcohols are more polar, the sulfinate containing fractions of the initial Chromatographic separations usually contain some alcohol. The troublesome, labile hydrolytic behavior of PMBCl has literature precedent; see ref. 12.
24. Baudin, J.-B.; Julia, S.A.; Wang, J. Synlett 1992, 911-913.