title: Nickel/Lewis acid-catalyzed cyanoesterification and cyanocarbamoylation of alkynes.
abstract: Cyanoformates and cyanoformamides are found to add across alkynes by nickel/Lewis acid (LA) cooperative catalysis to give beta-cyano-substituted acrylates and acrylamides, respectively, in highly stereoselective and regioselective manners. The resulting adducts serve as versatile synthetic building blocks through chemoselective transformations of the ester, amide, and cyano groups as demonstrated by the synthesis of typical structures of beta-cyano ester, beta-amino nitrile, gamma-lactam, disubstituted maleic anhydride, and gamma-aminobutyric acid. The related reactions of cyanoformate thioester and benzoyl cyanide, on the other hand, are found to add across alkynes with decarbonylation in the presence of a palladium/LA catalyst.
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: Akira
authors.initials: A
authors.lastname: Yada
authors.forename: Eiji
authors.initials: E
authors.lastname: Morita
authors.forename: Yoshiaki
authors.initials: Y
authors.lastname: Nakao
authors.forename: Tamejiro
authors.initials: T
authors.lastname: Hiyama
authors.forename: Masato
authors.initials: M
authors.lastname: Ohashi
authors.forename: Sensuke
authors.initials: S
authors.lastname: Ogoshi