Photoredox-Catalyzed Site-Selective α-C(sp3)-H Alkylation of Primary Amine Derivatives

The synthetic utility of tertiary amines to oxidatively generate a-amino radicals is well established, however, primary amines remain challenging because of competitive side reactions This report describes the site-selective a-functionalization of primary amine derivatives through the generation of a-amino radical intermediates. Employing visible-light photo-redox catalysis, primary sulfonamides are coupled with electron-deficient alkenes to efficiently and mildly construct C-C bonds. Interestingly, a divergence between intermolecular hydrogen-atom transfer (HAT) catalysis and intramolecular [1,5] HAT was observed through precise manipulation of the protecting group. This dichotomy was leveraged to achieve excellent alpha/delta site-selectivity.