Rhodium(II)-Catalyzed CH Insertions with imino>phenyl-λ3-iodane

Article abstract of DOI:10.1002/hlca.19970800407

The catalyzed decomposition of <<(4-nitrophenyl)sulfonyl>imino>phenyl-λ³-iodane (NsN=IPh) resulted in formal insertions into CH bonds, activated by phenyl or vinyl groups, or by O-substituents.Scope and limitations of the reaction were investigated.Yields of up to 84percent were achieved in the most favorable cases.Yields were enhanced by electron-releasing substituents and decreased by steric hindrance.Aziridination competed with allylic insertion with olefinic substrates.The insertion reaction proceeded with retention of configuration.With chiral Rh^II catalysts, a modest asymmetric induction was observed.A mechanism involving direct insertion by a Rh-complexed nitrene into the CH bond is proposed.