Combination of a Cyano Migration Strategy and Alkene Difunctionalization: The Elusive Selective Azidocyanation of Unactivated Olefins

Abstract A conceptually new, efficient, and metal‐free approach for the challenging azidocyanation of unactivated alkenes is presented. The strategy of intramolecular distal cyano migration is combined with alkene difunctionalization for the first time. A variety of useful azido‐substituted alkyl nitriles are prepared in good yields and, most importantly, with exquisite regio‐ and stereo‐selectivities.