Handbook of Grignard Reagents

Gary S. Silverman, Philip E. Rakita

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.