ELECTROCHEMICAL AND CHEMICAL REDUCTIVE SILYLATION OF ALIPHATIC NITRILES - A NEW ACCESS TO ALPHA-(SILYL)ALKYLAMINES

A general and efficient synthesis of the title amines (6) is described which consists in the electroreductive silylation of nitriles (1), fo llowed, in a one pot process, by the protonolysis of the silazanes (2, 3) and acylsilane enamines (8) formed and hydride reduction of the in termediate iminium salt. Formation of acylsilane enamines is interpret ed as the result of the reductive silylation of the ketenimine form of the nitriles whereas formation of silazanes is interpreted as the res ult of the reductive silylation of the nitrile function itself. A prel imary study of the electroreductive silylation of a N-(trimethylsilyl) aldimine, yielding a title amine after protonolysis of the intermediat e silazane, is also reported. Some of the silazanes presented particul ar nmr properties which were interpreted as being indicative of a conf ormationally locked structure.