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

Article abstract of DOI:10.1002/cctc.202000309

The well-defined three coordinated electronically unsaturated cationic organoaluminum complex [({(2,6-iPr₂C₆H₃N)P(Ph₂)}₂N)AlMe]⁺[MeB(C₆F₅)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.