title: Heteroatom-directed alkylcyanation of alkynes.
abstract: Alkanenitriles having a heteroatom such as nitrogen, oxygen, and sulfur at the gamma-position are found to add across alkynes stereo- and regioselectively by nickel/Lewis acid catalysis to give highly substituted acrylonitriles. The heteroatom functionalities likely coordinate to the nickel center to make oxidative addition of the C-CN bonds of the alkyl cyanides kinetically favorable, forming a five-membered nickelacycle intermediate and, thus, preventing beta-hydride elimination to allow the alkylcyanation reaction.
authors.affiliation: Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan. yoshiakinakao@npc05.mbox.media.kyoto-u.ac.jp
authors.forename: Yoshiaki
authors.initials: Y
authors.lastname: Nakao
authors.forename: Akira
authors.initials: A
authors.lastname: Yada
authors.forename: Tamejiro
authors.initials: T
authors.lastname: Hiyama
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D009570:Nitriles / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D000480:Alkynes; D009570:Nitriles