A new method for the bromosulfonamidation of olefins using a combination of S, S-dimethyl-N-(p-toluenesulfonyl)sulfilimine and N-bromosuccinimide is disclosed herein.Sulfilimines 1, which have the IUPAC name "sulfimide" remain less explored as synthetic reagents, 1 as compared with the analogous sulfoxides 2, which have found broad use in the area of stereoselective synthesis. 2 There has recently been a resurgence of interest, reflected in the reports regarding the synthesis of enantiomerically enriched sulfilimines 3 and their applications. 4 To the best of our knowledge, in all the chemistry of sulfilimines reported so far, the sulfimide moiety (S=NR) does not participate in the reaction. We disclose herein, a transformation wherein the sulfimide moiety functions as a nucleophile in the N-bromosuccinimide (NBS) promoted, bromosulfonamidation of alkenes.The vicinal halo amine functionality is a structural unit of importance in synthetic organic chemistry. 5 A number of synthetic approaches have been developed to secure this functionality. N,N-Dihalo sulfonamides, 6 N-halo carbamates, 7 N,N-dihalo carbamates, 8 N,N-dibromo phosphoramidate, 9 halo azide, 10 halogen isocyanates, 11 cyanamide/ NBS, 12 sulfonamide/iodonium bis-sym-collidine perchlorate, 13 are the reagents which effect the transformation of alkenes to products with a halo amine moiety. These methods are not without limitations. The reaction of dihalo sulfonamides is not general and straightforward. The products resulting from dihalo sulfonamides and dihalo carbamates have a nitrogen-halogen bond which is to be reduced. The N-halo carbamates require stoichiometric quantities of metal halide as promoters. The dihalo phosphoramidates are not readily available and the halo azides suffer from the drawback of not being easily handled. The utility of the sulfonamide-I + combination has been demonstrated for glycals only. The study of highly regio-and stereoselective amino halogenation of olefins therefore still remains important and challenging.Drawing a parallel with the reactivity of dimethyl sulfoxide with alkenes initiated by NBS, 14 we decided to explore the reaction of alkenes with NBS using S,S-dimethyl-N-(p-toluenesulfonyl)sulfilimine, as the nucleophile (Scheme 1). Scheme 1The results of the study are summarized in Table. S,SDimethyl-N-Ts-sulfilimine was prepared from dimethyl sulfide and Chloramine-T by the Mann-Pope reaction. 15 Dichloromethane and chloroform were found to be the solvents of choice for the reaction. 16 The reaction probably proceeds by an ionic mechanism which would explain the observed regioselectivity; the nucleophilic attack taking place at the carbon atom (anomeric and benzylic) best able to stabilize a partial positive charge. Triacetyl-D-glucal 3, afforded product 4 as the only bromosulfonamide, while related substrate 5, yielded sulfonamides 6 and 7 in a 2: 1 ratio. Dihydropyran afforded isomers 9 and 10. The structures were assigned to the products by comparing their 1 H NMR data with literature values of known (9, 10...

Bromohydrins have been prepared from beta-methyl-gamma,delta-unsaturated sulfoxides with high regio- and stereoselectivity. The reaction proceeds via neighboring group participation of the sulfinyl moiety with inversion of sulfoxide configuration as proven by an (18)O labeling study and X-ray crystallography.

A stereoselective synthesis of (-)-galantinic acid is disclosed. The key steps include hydrolytic kinetic resolution of a racemic epoxide and regio- and stereoselective heterofunctionalization of an olefin, using a pendant sulfinyl group as the nucleophile. The participation of the sulfinyl group was unambiguously proven by conducting the reaction in the presence of H(2)(18)O.

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