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

ABSTRACT: The synthetic utility of tertiary amines to oxidatively generate ?-amino radicals is well established, however, primary amines remain challenging because of competitive side reactions. This report describes the site-selective ?-functionalization of primary amine derivatives through the generation of ?-amino radical intermediates. Employing visible-light photoredox 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 ?/? site-selectivity.

SUBMITTER: Ashley MA 

PROVIDER: S-EPMC6442930 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature