title: Catalytic reactions of titanium alkoxides with Grignard reagents and imines: a mechanistic study.
abstract: The reactivity of Grignard reagents towards imines in the presence of catalytic and stoichiometric amounts of titanium alkoxides is reported. Alkylation, reduction, and coupling of imines take place. Whereas reductive coupling is the major reaction in stoichiometric reactions, alkylation is favored in catalytic reactions. Mechanistic studies clearly indicate that intermediates involved in the two reactions are different. Catalytic reactions involve a metal-alkyl complex. This has been confirmed by reactions of deuterium-labeled substrates and different alkylating agents. Under the stoichiometric conditions, however, titanium olefin complexes are formed through reductive elimination, probably through a multinuclear intermediate.
authors.affiliation: Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, 560012, India.
authors.forename: Akshai
authors.initials: A
authors.lastname: Kumar
authors.forename: Ashoka G
authors.initials: AG
authors.lastname: Samuelson
mesh_terms: D000478:Alkylation; D002384:Catalysis; D007097:Imines / Q000737:chemistry*; D007553:Isotope Labeling; D009682:Magnetic Resonance Spectroscopy; D009942:Organometallic Compounds / Q000737:chemistry*
chemical_list: D007097:Imines; D009942:Organometallic Compounds; C102815:titanium isopropoxide