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

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.