Transition metal-catalyzed asymmetric carbene insertion for synthesis of chiral amines

Chiral amines are an important class of organic compounds. They ubiquitous in chemistry and often serve as fundamental building blocks, versatile synthons, efficient chiral catalysts, ligands or auxiliaries asymmetric synthesis medicinal chemistry. During the past few decades, there has been remarkable progress development methods. Accordingly, synthesis, particularly catalytic enantioselective received considerable attention from both academia industry. Among them, transition metal-catalyzed carbene insertion emerged one most useful powerful methods for various through construction C−N bonds. In this review, we present advances that have made using copper, rhodium, palladium, iron catalysts to perform N−H reactions with diazo An overview early examples Cu(I) Ag(I)-bisoxazoline-catalyzed subsequent developments by copper(I) complexes spiro bisoxazolines, bipyridines binol derivatives, well rhodium(II)-, palladium(II)-, iron(II)-carbene is provided. these work, metal-carbene into bond aromatic amines, amides (BocNH2, CbzNH2), substituted carbazoles indoles, benzophenone imines were achieved under mild reaction conditions, allowing access a wide variety structurally enantiomerically enriched form. particular, use α-aryl α-alkyl α-diazoesters precusors, aryl alkyl α-amino esters could be prepared good yields high enantioselectivities. A recent major breakthrough transition-metal-catalyzed aliphatic also discussed. By combination achiral copper complex amino-thiourea catalyst, highly bonds was produce acid derivatives bearing secondary tertiary amino substituents yields. Overall, review summarizes prominent work on their applications natural unnatural synthesis.