Energy-Transfer-Enabled Chemoselective Carboimination and Carboiminoxylation of Alkenes Using a Simple Oxime

Abstract

Visible-light activation of activated oximes has found wide applications in alkene 1,2-difunctionalization. Previous studies relied on photochemical cleavage of the weak N–O bond in activated oximes to generate a persistent iminyl radical together with a partner radical, enabling the simultaneous installation of an imino group and a second fragment across an alkene. Herein, by selectively cleaving either the N–O bond or the O–H bond in oximes, we introduce a unified strategy for the chemoselective carboimination or carboiminoxylation of alkenes. Using benzophenone-derived oximes with readily available alkenes and alkynes under phosphine catalysis and energy-transfer (EnT) photocatalysis, the method provides rapid access to either N- or O-functionalized β-ketoester derivatives. More broadly, this approach opens an avenue to selectively install different heteroatoms from a simple oxime onto unsaturated substrates and is particularly valuable for alkene functionalization.