STEREOCHEMISTRY OF SULPHILIMINE AND SULPHOXIDE FORMATIONS IN REACTIONS OF SULPHIDES WITH CHLORINATING AGENTS AND NUCLEOPHILES

Article abstract of DOI:10.1016/S0040-4020(01)83133-1

The stereochemistry of sulphilimine and sulphoxide formations was studied in reactions of chiral alkyl aryl sulphides either with N-chloro toluenesulphonamides or with t-BuOCl followed by TsNH^-Na⁺ both leading to unequal amounts of diastereomers of products.Configurations were determined by spectroscopic methods and stereospecific reactions, and diastereomeric product distributions were measured by hplc.Results are discussed and reaction pathways are suggested for-the product controlling steps.From sulphonium type intermediates sulphoxides are formed by hydrolysis with inversion, while sulphilimines with retention or inversion of configuration at sulphur depending on manner of attack by N-nucleophile.In reactions of ortho-carboxy-substituted sulphides both sulphilimines and sulphoxides are formed from cyclic acyloxysulphonium intermediates with inversion of configuration at sulphur.