title: Cyanoesterification of 1,2-dienes catalyzed by nickel.
abstract: Cyanoformate esters add across 1,2-dienes in the presence of a nickel/PMe(2)Ph catalyst to afford beta-cyano-alpha-methylenealkanoates regioselectively, which are kinetically favored and readily isomerize to thermodynamically favored alpha-cyanomethyl-alpha,beta-unsaturated carboxylates at high temperature under the nickel catalysis, possibly through oxidative addition of the C-CN bond. Similar cyanoesterification products are produced from chloroformate esters, trimethylsilyl cyanide, and 1,2-dienes in the presence of a nickel/dppp catalyst. The resulting cyanoesterification products have a structure of allylic cyanide and thus undergo further allyl cyanation reaction across alkynes with the aid of a nickel/P(4-CF(3)-C(6)H(4))(3) catalyst to afford highly substituted acrylonitrile derivatives.
authors.affiliation: Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan.
authors.forename: Yasuhiro
authors.initials: Y
authors.lastname: Hirata
authors.forename: Tomohiko
authors.initials: T
authors.lastname: Inui
authors.forename: Yoshiaki
authors.initials: Y
authors.lastname: Nakao
authors.forename: Tamejiro
authors.initials: T
authors.lastname: Hiyama