Nitriles with organometallic

The most general synthetic route to ketones uses the reaction of carboxylic acids (or their derivatives) or nitriles with organometallic compounds (M.J. Jorgenson, 1970). Lithium car-boxylates react with organolithium compounds to give stable gem-diolates, which are decom-... 

Reaction of Nitriles with Organometallic Reagents Grignard reagents add to a nitrile to give an intermediate imine anion that is hydrolyzed by addition of water to yield a ketone. 

Nitriles are similar in some respects to carboxylic acids and are prepared either by SN2 reaction of an alkyl halide with cyanide ion or by dehydration of an amide. Nitriles undergo nucleophilic addition to the polar C=N bond in the same way that carbonyl compounds do. The most important reactions of nitriles are their hydrolysis to carboxylic acids, reduction to primary amines, and reaction with organometallic reagents to yield ketones. 

Addition of C-nucleophiles to nitrile oxides is of special interest. There are examples of reactions with both carbanions and neutral carbon nucleophiles. To the former group belong reactions of nitrile oxides with organometallic... 

In this book we are not concerned with organometallic reactivity of compounds containing M-C bonds, and so to all intents and purposes this section is about the reactions of nitriles or cyanides with nucleophiles. Reactions of co-ordinated alkynes are adequately discussed elsewhere. 

Few reagents are available for the preparation of organometallic and coordination complexes of the early transition metals. The anhydrous metal halides often lead to disproportionation reactions, and the nitrile derivatives,1 MX (NCR)>, are not suitable because of the reactivity of the nitrile with many other reagents. The procedures described below provide simple, high-yield routes to the tetrahydrofuran (THF) complexes of selected, early transition metal halides.2 They have been useful for the synthesis of a wide variety of organometallic complexes.3... 

FIGURE 18.47 (a) Reaction of a nitrile with an organometallic reagent gives an imine salt. Acidification first... 

Leung CV, Zheng W, Zhou Z, Lin Z, Lau CP. Mechanism of catalytic hydration of nitriles with hydrotris(pyrazolyl)borato (Tp) mthenium complexes. Organometallics. 2008 27 4957-4969. 

The reactions of nitriles with water, hydride, and organometallic reagents as nucleophiles are as follows ... 

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