Product-catalyzed addition of alkyl nitriles to unactivated imines promoted by sodium aryloxide/ethyl(trimethylsilyl)acetate (ETSA) combination.

The first transition-metal-free addition of alkyl nitriles to unactivated imines was developed using a catalytic combination of 4-MeOC(6)H(4)ONa and TMSCH(2)CO(2)Et to promote the reaction. The corresponding beta-amino nitriles are obtained in good to almost quantitative isolated yields under mild conditions. A mechanism involving an autocatalytic pathway is proposed on the basis of experimental observations.