Enantioselective Scandium-Catalyzed Benzylic C−H Addition of Tertiary Anilines to Alkenes

Abstract

Enantioselective C−H addition of aromatic amines to alkenes represents a highly efficient and direct approach for the synthesis of chiral alkylanilines. Herein, we report an enantioselective benzylic C(sp3)−H addition of tertiary anilines to alkenes, enabled by a bulky anilido-oxazoline ligand-supported scandium catalyst. This protocol delivers a broad range of chiral alkylated anilines in high yields (up to 96%) and enantioselectivities (up to 98:2 e.r.). Furthermore, the obtained tertiary anilines are able to undergo facile C−N bond cleavage to afford enantioenriched aryl boronic esters and aryl silanes, serving as versatile intermediates for the synthesis of further functionalized, high-value molecules. The origins of chemo- and enantioselectivity in this transformation have been investigated through density functional theory calculations.