Silver‐Catalyzed Cross‐Coupling of Isocyanides and Active Methylene Compounds by a Radical Process

Abstract Isocyanides are versatile building blocks, and have been extensively exploited in CH functionalization reactions. However, transition‐metal‐catalyzed direct CH functionalization reactions with isocyanides suffer from over‐insertion of isocyanides. Reported herein is a radical coupling/isomerization strategy for the cross‐coupling of isocyanides with active methylene compounds through silver‐catalysis. The method solves the over‐insertion issue and affords a variety of otherwise difficult to synthesize β‐aminoenones and tricarbonylmethanes under base‐ and ligand‐free conditions. This report presents a new fundamental CC bond‐forming reaction of two basic chemicals.