Chemoselective Silylative Reduction of Conjugated Nitriles under Metal‐Free Catalytic Conditions: β‐Silyl Amines and Enamines

The B(C6F5)3‐catalyzed silylative reduction of conjugated nitriles has been developed to afford synthetically valuable β‐silyl amines. The reaction is chemoselective and proceeds under mild conditions. Mechanistic elucidation indicates that it proceeds by rapid double hydrosilylation of the conjugated nitrile to an enamine intermediate which is subsequently reduced to the β‐silyl amine, thus forming a new C(sp3)Si bond. Based on this mechanistic understanding, a preparative route to enamines was also established using bulky silanes.