Aminomethylation Reaction of ortho-Pyridyl C-H Bonds Catalyzed by Group 3 Metal Triamido Complexes

作者：Nagae Haruki; Shibata Yu; Tsurugi Hayato^*; Mashima Kazushi

来源：Journal of the American Chemical Society, 2015, 137(2): 640-643.

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](2)Y(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.

• 出版日期2015-1-21