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.