Deconstructive Radical–Radical Coupling for Programmable Remote Acylation

Abstract Dicarbonyl compounds are structural motifs that have been extensively utilized in synthetic chemistry, and their downstream transformations have proven valuable in synthesizing numerous heterocycles. Conventional methods for accessing such compounds include the Stetter reaction, the Michael reaction, and Friedel–Crafts acylation. However, a flexible and enabling platform for obtaining all types of 1,n‐dicarbonyls remains undeveloped. Reported herein is a unified approach to access a variety of 1,n‐dicarbonyls through a radical‐promoted deconstructive process utilizing dual photocatalysis/carbene catalysis. The utility of this strategy is demonstrated with a broad scope with robust functional group tolerance along with application in the preparation of γ‐amino esters, three‐component manifolds, and the first enantioselective deconstructive synthesis of 1,5‐dicarbonyls using a chiral NHC catalyst.