title: Aminomethylation reaction of ortho-pyridyl C-H bonds catalyzed by group 3 metal triamido complexes.
abstract: 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.
authors.affiliation: Department of Chemistry, Graduate School of Engineering Science, Osaka University and CREST, JST , Toyonaka, Osaka 560-8531, Japan.
authors.forename: Haruki
authors.initials: H
authors.lastname: Nagae
authors.forename: Yu
authors.initials: Y
authors.lastname: Shibata
authors.forename: Hayato
authors.initials: H
authors.lastname: Tsurugi
authors.forename: Kazushi
authors.initials: K
authors.lastname: Mashima
mesh_terms: D000577:Amides / Q000737:chemistry*; D002384:Catalysis; D007097:Imines / Q000737:chemistry; D007700:Kinetics; D008745:Methylation; D009942:Organometallic Compounds / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*
chemical_list: D000577:Amides; D007097:Imines; D009942:Organometallic Compounds; D011725:Pyridines; C023666:pyridine