Ag eneral and efficient rhodium-catalyzed asymmetric cyanide-free hydrocyanation of alkenes has been developed. Based on the asymmetric hydroformylation/condensation/aza-Cope elimination sequences,abroad scope of substrates including mono-substituted, 1,2-, and 1,1-disubstituted alkenes (involving natural product R-and S-limonene) were employed, and as eries of valuable chiral nitriles are prepared with high yields (up to 95 %) and enantioselectivities (up to 98 %ee). Notably,t he critical factor to achieve high enantioseletivies is the addition of catalytic amount of benzoic acid. This novel methodology provides an efficient and concise synthetic route to the intermediate of vildagliptin and anagliptin.Scheme 1. DuPont'sp roduction of adiponitrile by hydrocyanation.Scheme 2. Transition-metal-catalyzed hydrocyanation of alkenes.