Cyanoesterification of 1,2-dienes: synthesis and transformations of highly functionalized alpha-cyanomethylacrylate esters.
A Ni/PMe2Ph catalyst is found to effect regioselective addition of cyanoformate esters across 1,2-dienes, giving rise to 3-alkoxycarbonyl-3-butenenitriles. Functional groups such as cyano, protected hydroxyl, and amino groups in the 1,2-diene substrates are tolerated. Isomerization of the initial products to thermodynamically more stable isomers takes place possibly through further oxidative addition of the C-CN bond of 3-alkoxycarbonyl-3-butenenitriles to Ni(0) followed by reductive elimination. The cyanoesterification products undergo further addition across alkynes in the presence of a Ni/P(4-CF3-C6H4)3 catalyst.
Nakao
Yoshiaki
Y
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan. nakao@npc05.kuic.kyoto-u.ac.jp
Hirata
Yasuhiro
Y
Hiyama
Tamejiro
T
D000466:Alkadienes / Q000737:chemistry*; D002384:Catalysis; D003485:Cyanates / Q000737:chemistry*; D004952:Esters / Q000737:chemistry*; D007536:Isomerism; D008689:Methacrylates / Q000138:chemical synthesis*; D008956:Models, Chemical; D009570:Nitriles / Q000138:chemical synthesis*; D028561:Transition Elements / Q000737:chemistry
D000466:Alkadienes; D003485:Cyanates; D004952:Esters; D008689:Methacrylates; D009570:Nitriles; D028561:Transition Elements