Aminoalkylation reaction of ortho-pyridyl C-H bond was catalyzed by group 3 metal amido complexes, M[N(SiMe3)2]3. Among them, we found that Gd[N(SiMe3)2]3 showed the highest catalytic activity, and secondary amines such as dibenzylamine dramatically improved the catalytic activity. This is the first example of catalytic C-H bond functionalization by using group 3 metal amido complexes. A mixed ligated complex, [(Me3Si)2N]2Y(NBn2)(THF) (4), was isolated as a catalytically active species. Kinetic study using the complex 4 revealed a plausible reaction mechanism (Scheme 1), where the metal-nitrogen bond of amido complex A activated an ortho-C-H bond of pyridine derivs. to form 3-membered azametallacycle C and amine via five-coordinated intermediate B, and then the coordinated pyridine was exchanged to imines to form D, and subsequent insertion of the imine into the metal-carbon bond proceeded to afford 5-membered diazametallacycle E. [on SciFinder(R)]
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