Photoredox-catalyzed oxygen-centered radical-mediated α-alkoxycarbonyloxylation of ketones

Abstract

Herein, we report a visible-light photoredox-catalyzed α-alkoxycarbonyloxylation of ketones using pyridinium-derived alkoxycarbonyloxyl radicals (ACORs). Selective addition of photo-generated ACORs to enol esters affords a broad range of α-alkoxycarbonyloxylated products under mild conditions. This method shows excellent compatibility with aromatic and aliphatic enol esters, including complex natural products, and the resulting products can be readily hydrolyzed to α-hydroxy ketones. This protocol provides a practical, mild, and complementary route to α-oxygenated carbonyl compounds and expands the synthetic application of oxygen-centered radicals.