Stereochemical Models for Rh-Catalyzed Amination Reactions of Chiral Sulfamates

Abstract
Oxidative C−H amination of chiral sulfamate esters using achiral Rh-carboxylate catalysts, PhI(OAc)2, and MgO occurs in high yield and with good to excellent diastereocontrol. A number of examples are included to support a proposed transition state model that accounts for the observed stereoinduction. In addition, stereoselective intramolecular aziridination with substituted homoallyl sulfamates is demonstrated and is rationalized through an analogous stereochemical construct.