Advances in Palladium-Catalyzed Imidoylative Cyclization Reaction of Functionalized Isocyanides
Significant progress has been made in palladium-catalyzed isocyanide insertion reactions in recent years.Notably,the development of imidoylative cyclization reactions of functionalized isocyanides with tunable substituents on isocyanide groups has opened a novel pathway for synthesizing various nitrogen-containing heterocycles.This review primarily summarizes palladium-catalyzed imidoylation and cyclization reactions of functionalized isocyanides,emphasizing recent advances in asymmetric catalysis.Functionalized isocyanides undergo migratory insertion into Ar—Pd bonds,forming imidoyl palladium intermediates,while functional groups introduced within the isocyanide structure capture these intermediates,facilitating the construction of achiral nitrogen-containing heterocycles.The review highlights three strategies for capturing imidoyl palladium intermediates to construct achiral heterocycles:nucleophilic reagents,C—H bonds,and unsaturated bonds.Moreover,the use of functionalized isocyanide insertion strategies has enabled enantioselective palladium-catalyzed isocyanide insertion reactions.The review discusses the development of enantioselective chiral heterocycle synthesis involving central chirality,planar chirality,axial chirality,and inherent chirality.