I. Nageli et al., RHODIUM(II)-CATALYZED CH INSERTIONS WITH NITROPHENYL)SULFONYL]IMINO)PHENYL-LAMBDA(3)-IODANE, Helvetica Chimica Acta, 80(4), 1997, pp. 1087-1105
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.