Intramolecular arylcyanation across a tri-substituted double bond proceeds to give a primary alkyl cyanide product through functionalization of C-CN and allylic C-H bonds and double C-C bond formation in a 1,3-manner by cooperative nickel/AlMe2Cl catalysis. The transformation is applied to the synthesis of rhazinilam, a tubulin-binding alkaloid containing unique structural motifs such as axially chiral biaryl and strained nine-membered lactam as well as quaternary carbon. (C) 2015 Elsevier Ltd. All rights reserved.