Optical resolution of H/D isotopic chirality via asymmetric C–H amination

Isotopic chirality arising from hydrogen/deuterium substitution has long resisted optical resolution because isotopic substitution introduces only minimal stereochemical differences, rendering such molecules structurally pseudo-achiral. Recognizing that the small yet distinct difference in C–H/C–D bond dissociation energies (BDEs) creates an energetic asymmetry, we envisioned that an enantioselective C–H functionalization exploiting this disparity could achieve the kinetic resolution of isotopically chiral molecules. Here, we report a catalytic method for the optical resolution of benzylic and allylic H/D isotopic chirality. This method achieved a remarkably high separation factor ( S = 83.1), enabling the isolation of highly enantioenriched isotopically chiral substrates from racemic mixtures and revealing retention of stereochemical memory during radical recombination in asymmetric C–H functionalization.