Basicity reaction with Grignard reagents

Nitriles are synthetically versatile functional groups because they are readily converted to carboxylic acids by hydrolysis under addic or basic conditions, reduced with LiAlH4 to form primary amines, and reaction with Grignard reagents leads to the formation of ketones. These reactions are illustrated here ... 

The reaction of Grignard reagents and organolithium compounds with aldehydes and ketones is perhaps the most useful method for the preparation of alcohols. The reaction is conducted under basic conditions and proceeds according to the following general mechanism ... 

The (dienyl)iron cations of type (248) and (265) are susceptible to reaction with nucleophiles. For the (cyclohexadienyl)iron cations, nucleophilic attack always occurs at a terminal carbon, on the face of the ligand opposite to the metal, to afford / -cyclohexadiene products. Typical nucleophiles used are malonate anions, amines, electron-rich aromatics, silyl ketene acetals, enamines, hydrides, and aUyl silanes intramolecular nucleophilic addition is also possible. The addition of highly basic organometaUic nucleophiles (Grignard reagents, organolithiums) is often problematic this may be overcome by replacing one of the iron carbonyl... 

Thiophenethiols are prepared by reduction of the sulfonyl chlorides or, more conveniently, by the reaction of Grignard reagents or thienyllithium compounds with sulfur. They have also been obtained by cleavage or thienyl alkyl sulfides with sodium in liquid ammonia. 3-Thiophenethiol is a by-product in the commercial thiophene synthesis. Thiophenethiols have recently also been prepared by a synthesis involving Friedel-Crafts reaction of 2,4-dinitrobenzenesulfenyl chloride with thiophenes, followed by basic cleavage of the resulting sulfide. ... 

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