1st Edition

Handbook of Grignard Reagents

By Gary S. Silverman, Philip E. Rakita Copyright 1996

    This handbook provides the theoretical and practical information necessary to explore new applications for Grignard reagents on a day-to-day basis, presenting a comprehensive overview of current research activities in Grignard chemistry. This book surveys specific reactions and applications of Grignard reagents, organized by type of substrate and the general category of reaction. It also summarizes the spectrum of reactions exhibited by Grignard reagents.

    Part 1 Methods of Grignard reagent preparation: common method of Grignard reagent preparation; preparation of Grignard reagents from olefins and acetylenes; magnesium activation. Part 2 Safe handling practices: safe handling practices of industrial scale Grignard reagents. Part 3 Analyses of Grignard reagents: wet analyses of Grignard reagents; infrared and raman spectroscopy; nuclear magnetic resonance analysis of Grignard reagents; crystal structures of Grignard reagents. Part 4 Mechanisms and structure-reactivity relationships: mechanism of Grignard reagent formulation; mechanism of reactions in Grignard reagents; structure-reactivity relationships; the composition of Grignard reagents in solution - the Schlenk equilibrium and its effect on reactivity; effect of tris(pyrazolyl)hydrobotato ligation. Part 5 General reactions of Grignard reagents: nucleophilic substitution with electrophilic organic, main group and transition metal species; nucleophilic addition to unconjugated C-C multiple bond; nucleophilic addition of C-C multiple bonds - O, S, N, P; nucleophilic addition to conjugated carbon-carbon bonds; nucleophilic addition to conjugated carbon-heteroatom multiple bonds - O, S, N; nucleophilic addition to organometallic vinylidene and allyl complexes. Part 6 Special topics - applications and reactions of Grignard reagents: the Barbier reaction; Grignard reagents as bases; Sn2 versus Sn21; dihalide-derived di-Grignard reagents - preparation and reactions; formation and reactions of substituted (2-butene-1,4-diyl)magnesium complexes; spiroannulations using substituted (2-butene-1,4-diyl)magnesium complexes; asymmetric synthesis using Grignard reagents; metal-catalyzed reactions; the preparation of 1,1-bimetallics of magnesium and zinc; alkynyl Grignard reagents and their uses; Grignard reagents and silanes; Ziegler-Natta catalysis; organomagnesium compounds as polymerization initiators.


    Gary S. Silverman, Philip E. Rakita