Heteroatom-directed alkylcyanation of alkynes.
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.
Nakao
Yoshiaki
Y
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan. yoshiakinakao@npc05.mbox.media.kyoto-u.ac.jp
Yada
Akira
A
Hiyama
Tamejiro
T
D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D009570:Nitriles / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
D000480:Alkynes; D009570:Nitriles