A new reaction of 2-(phenylsulfonyl)-3-phenyloxaziridine (davis reagent): Oxidation of thiolates to sulfinates. Application to the synthesis of sulfones

Organic Letters

Volumn 1, Issue 8, 1999, Pages 1177-1180

  Sandrinelli, Franck ^a   Perrio, Stéphane ^a   Beslin, Pierre ^a  

^a UNIVERSITÉ DE CAEN   (France)

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EID: 0000449359     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol990170k     Document Type: Article

References (62)

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9. This aromatic thiol was used for much of the initial work owing to its ease of handling (not malodorous, relatively high molecular weight).
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12. 2Ph derived from the oxaziridine was present in the crude product. Small amounts of benzaldehyde and benzenesulfonamide, resulting from partial hydrolysis of the imine on workup, were also detected.
13. 9b thiolates. The oxidants employed were respectively dimethyldioxirane and m-CPBA: (a) Schenk, W. A.; Frisch, J.; Adam, W.; Prechtl, F. Inorg. Chem. 1992, 31, 3329-3331.
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15. Sulfinates are ambident nucleophiles. With soft electrophiles such as alkyl halides, the alkylation occurs predominantly at sulfur to give sulfones: Simpkins N. S. Sulphones in Organic Synthesis; Baldwin, J. E., Magnus P. D., Eds.; Pergamon Press: Oxford, 1993; Vol. 10, pp 11-15.
16. The failure of the alkylation reaction of lithium alkenylsulfinate salts with THF as solvent has already been reported: Dishington, A. P.; Douthwaite, R. E.; Mortlock, A.; Muccioli, A. B.; Simpkins, N. S. J. Chem. Soc., Perkin Trans. 1 1997, 323-337.
17. a value of benzenesulfinic acid is 1.29:
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23. For a mild and simple preparation of sulfinates, sulfonyl chlorides, and sulfonamides from thioanisoles, see: De Vleeschauwer, M.; Gauthier, J. Y. Synlett 1997, 375-377.
24. Reported oxidation reactions with oxygen or superoxide anion suffer from at least one of the following drawbacks: lack of selectivity with formation of other unwanted oxidation products alongside the anticipated sulfinate or requirement of unusual conditions (for example, electrochemical generation of thiolates or use of resin-supported arenethiolates): (a) Claessen, P. J. Prakt. Chem. 1877, 15, 193-222.
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33. The analogous reaction, in nonbasic conditions, has been investigated with considerable success. Direct oxidation of aliphatic and aromatic thiols with 2 equiv of m-CPBA afforded the corresponding sulfinic acids in high purity and good yield: (a) Filby, W. G.; Günther, K.; Penzhorn, R. D. J. Org. Chem. 1973, 38, 4070-4071. More recently, dimethyldioxirane was found to be a very effective oxidant for aliphatic thiols, though a variety of other oxidation products were isolated when using benzylic or aromatic substrates:
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48. 2-Ph, resulting from addition of the intermediate sulfinic acid to the imine. See ref 13a.
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51. 13C NMR spectra are provided as Supporting Information.
52. We preferred to use toluene instead of benzene: Crandall, J. K.; Pradat, C. J. Org. Chem. 1985, 50, 1327-1329.
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60. Thiol 5f was prepared by heating 1,4-dichorobenzene with an excess of sodium ethanethiolate in refluxing DMF followed by acidification. See: Testaferri, L.; Tiecco, M.; Tingoli, M.; Chianelli, D.; Montanucci, M. Synthesis 1983, 751-755.
61. The oxidation of bis-sulfide 7 with 2 equiv of oxaziridine 1 led to a different result, with the formation of the bis-sulfoxide 8 in 89% yield. (Matrix Presented)
62. No dibenzyl sulfoxide or dibenzyl sulfone, even as trace amounts, was detected; the starting sulfide was recovered quantitatively after column chromatography.