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Catalytic Reactions of Titanium Alkoxides with Grignard Reagents and Imines:A Mechanistic Study

Kumar, Akshai and Samuelson, Ashoka G (2010) Catalytic Reactions of Titanium Alkoxides with Grignard Reagents and Imines:A Mechanistic Study. In: Chemistry - An Asian Journal, 5 (8). pp. 1830-1837.

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Official URL: http://onlinelibrary.wiley.com/doi/10.1002/asia.20...

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.

Item Type: Journal Article
Keywords: Alkylation; catalysis; Grignard reagents; isotopic labeling; titanium isopropoxide.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 08 Sep 2010 07:28
Last Modified: 20 Sep 2010 07:56
URI: http://eprints.iisc.ernet.in/id/eprint/32033

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