Aminomethylation reaction of Ortho -pyridyl C-H bonds catalyzed by group 3 metal triamido complexes

Article abstract of DOI:10.1021/ja511964k

Tris[N,N-bis(trimethylsilyl)amido] complexes of group 3 metals, especially yttrium and gadolinium, served as catalysts for ortho-C-H bond addition of pyridine derivatives and N-heteroaromatics into the C=N double bond of nonactivated imines to afford the corresponding aminomethylated products. Addition of catalytic amounts of secondary amines, such as dibenzylamine, dramatically improved the catalytic activity through the formation of a mixed ligated complex such as [(Me₃Si)₂N]₂Y(NBn₂)(THF) (4). Furthermore, kinetic studies using the isolated complex 4 provided a plausible reaction mechanism by which coordination of two pyridine derivatives afforded a penta-coordinated species as a key step.