ja511964k_si_001.pdf (4.57 MB)
Aminomethylation Reaction of ortho-Pyridyl C–H Bonds Catalyzed by Group 3 Metal Triamido Complexes
journal contribution
posted on 2015-01-21, 00:00 authored by Haruki Nagae, Yu Shibata, Hayato Tsurugi, Kazushi MashimaTris[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 CN 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.