Rhodium-Catalyzed Asymmetric Arylation of Cyclic N-Sulfonyl Aryl Alkyl Ketimines: Efficient Access to Highly Enantioenriched α-Tertiary Amines

A simple catalyst system of Rh(I)/sulfur-olefin with exceptional catalytic performance has been developed for the highly enantioselective arylation of cyclic N-sulfonyl aryl alkyl ketimines with arylboroxines/arylboronic acids. Optically active a-arylalkyl-substituted benzosultams and benzosulfamidates which are generally difficult to obtain were easily prepared with excellent stereocontrol (up to 99.9% ee). The synthetic utility of the approach was demonstrated by the facile construction of NMDA antagonist FR115427 and benzoxazinone derivatives. This protocol offers new opportunities for the efficient synthesis of diverse chiral a-tertiary amines.