RHODIUM(II)-CATALYZED CH INSERTIONS WITH NITROPHENYL)SULFONYL]IMINO)PHENYL-LAMBDA(3)-IODANE

The [Rh-2(OAc)(4)]-catalyzed decomposition of nitrophenyl)sulfonyl]imi no}phenyl-lambda(3)-iodane (NsN = IPh) resulted in formal insertions i nto CH bonds, activated by phenyl or vinyl groups, or by O-substituent s. Scope and limitations of the reaction were investigated. Yields of up to 84% were achieved in the most favorable cases. Yields were enhan ced by electron-releasing substituents and decreased by steric hindran ce. Aziridination competed with allylic insertion with olefinic substr ates. The insertion reaction proceeded with retention of configuration . With chiral Rh-II catalysts, a modest asymmetric induction was obser ved. A mechanism involving direct insertion by a Rh-complexed nitrene into the CH bond is proposed.