Organometallic reagents reactions with aldehydes

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, partial reduction to aldehydes, and reaction with organometallic reagents to yield ketones. 

The oxidation of alcohols to aldehydes and ketones by chromium(VI) reagents opens up important synthetic possibilities based on further reactions with organometallic reagents. 

The formation of chiral alcohols from carbonyl compounds has been fairly widely studied by reactions of aldehydes or ketones with organometallic reagents in the presence of chiral ligands. Mukaiyama et al. 1081 obtained excellent results (up to 94% e.e.) in at least stoichiometric addition of the chiral auxiliary to the carbonyl substrate and the organometallic reagent. 

Three different routes to the key compounds for the sila-Peterson elimination, the a-alkoxydisilanes 157, are described in the literature, namely A, reaction of silyllithium reagents with ketones or aldehydes B, addition of carbon nucleophiles to acylsilanes C, deprotonation of the polysilylcarbinols. In addition, method D, which already starts with the reaction of 2-siloxysilenes with organometallic reagents, leads to the same products. The silenes of the Apeloig-Ishikawa-Oehme type synthesized so far are summarized in Table 4. 

Desulfonylation of /7-silylvinyl sulfone 246 with Bu3SnLi followed by treatment with aldehydes affords y-hydroxy vinylsilanes 247 in good yields (equation 199)356. Reactions of trimethyl(2-nitrovinyl)silane with organometallic reagents give regioselectively... 

Reaction of organometallic reagents with aldehydes and ketones... 

Reaction of Organometallic Reagents with Aldehydes and Ketones... 

A diazonium salt reacts with copper(I) cyanide to form a benzonitrile. Because a cyano group can be hydrolyzed to a carboxylic acid, reduced to an amine or aldehyde, or converted to a ketone with organometallic reagents, this reaction provides easy access to a wide variety of benzene derivatives using chemistry described in Section 22.18. 

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