Excited-state cobaloxime catalysis enabled scalable oxidant-free dehydrogenative C–H phosphinoylation of undirected heterocycles†
Abstract
A visible-light-induced, synergistic excited-state cobaloxime catalysis system has been developed to perform the dehydrogenative C(sp2)–H phosphinoylation of various undirected bioactive molecules accompanied by H2 evolution. This protocol is conducted under oxidant-free conditions and is featured with high regioselectivity as well as a broad substrate scope (more than 60 examples; yields up to 90%). Notably, the successful achievement for the C(sp3)–H phosphinoylation of tetrahydroisoquinolines and the late-stage phosphinoylation of several marketed drugs further proves the potential synthetic utility of this approach. Mechanistic studies indicate that this transformation may proceed through a radical pathway.