Three Coordinated Organoaluminum Cation for Rapid and Selective Cyanosilylation of Carbonyls under Solvent‐Free Conditions

Abstract

Abstract The well‐defined three coordinated electronically unsaturated cationic organoaluminum complex [({(2,6‐ i Pr 2 C 6 H 3 N)P(Ph 2 )} 2 N)AlMe] + [MeB(C 6 F 5 ) 3 ] − ( 1 ), has been utilized to catalyze the cyanosilylation of aldehydes and ketones under mild and solvent‐free conditions. Moreover, catalyst 1 showed high chemoselective cyanosilylation of aldehydes over ketones, nitriles and olefins. The multinuclear NMR investigations revealed that cyanosilylation proceeds via Lewis adduct formation between 1 and TMSCN thereby activating TMSCN (Si‐CN bond) followed by nucleophilic attack of the carbonyl oxygen at the Si center of the activated silane and formation of the product.