Selective C−H Activation α to Primary Amines. Bridging Metallaaziridines for Catalytic, Intramolecular α-Alkylation

Selective α-C−H activation results in the synthesis of the first bridging metallaaziridine complex for the catalytic α-alkylation of primary amines. Reaction development led to the preparation of new Zr 2-pyridonate complexes for this useful transformation. No nitrogen protecting groups are required for this reaction, which is capable of assembling quaternary chiral centers α to nitrogen. Preliminary mechanistic investigations suggest bridging metallaaziridine species are the catalytically active intermediates for this α-functionalization reaction, while monomeric imido complexes furnish azepane hydroamination products.