Asymmetric imidation of organic selenides into selenimides

Treatment of aryl benzyl selenides with [N-(p-toluenesulfonyl)imino]phenyliodinane [TsN=IPh] in the absence or presence of copper(I) salt in toluene or acetonitrile affords the corresponding N-tosylselenimides in 31-46% yield. When the reaction is carried out in the presence of optically active 4,4'-disubstituted bis(oxazoline) as a ligand together with molecular sieves, enantioselective imidation occurs to give optically active N-tosylselenimides and the best result is obtained from benzyl 2-naphthyl selenide (64% yield and 36% ee). Similar treatment of allylic selenides gives the corresponding optically active allylic amides (up to 71% yield and 30%. ee). In the case of diastereoselective imidation, the reaction of diaryl selenides bearing a chiral oxazolinyl moiety with TsN=IPh or Chloramine-T trihydrate [TsN(CI)Na . 3H(2)O] has been successfully carried out to give the corresponding optically active N-tosylselenimides in good yields (up to 97%, isolated yield and 76% de). The absolute configuration around the selenium atom of (4S)-Se-[2-(4-isopropyloxazolin-2-yl)phenyl]-Se-phenyl-N-(p-toluenesulfonyl)selenimide [(4S)-13], obtained by diastereoselective imidation of the corresponding selenide with Chloramine-T trihydrate, has been determined to be S by X-ray crystallographic analysis, from the result of which an ionic reaction pathway involving a chloroselenonium ion intermediate is proposed. (C) 2000 Elsevier Science S.A. All rights reserved.