Atroposelective Synthesis of C–N Axially Chiral Biaryls via Catalytic C–H Functionalization at a Remote Site

Construction of axial chirality via distal functionalization consists of a significant challenge. Reported herein is the atroposelective synthesis of C-N axially chiral biaryls based on C-H bond activation at a site that is three bonds away from the axis atom. Under rhodium catalysis, naphthalimides bearing a bulky N-aryl group undergo carbonyl group-assisted C-H bond activation en route to alkynylation or alkenylation via desymmetrization or parallel kinetic resolution. Mechanistic studies indicate that C-H bond activation is likely enantiodetermining.