Nickel-catalyzed regioselective synthesis of tetrasubstituted alkene using alkylative carboxylation of disubstituted alkyne.
[Reaction: see text] Syntheses of alpha-silyl-beta,beta'-dialkyl alpha,beta-unsaturated carboxylic acids were achieved from silylated alkyne, carbon dioxide, and a zinc reagent using a catalytic amount of nickel complex in the presence of an excess amount of DBU. The regioselectivity of the introduction of CO2 into disubstituted alkyne is dependent on the electronic property of the substituent R on the alkyne because the thermodynamic stability of oxanickelacycle IV or V should be affected by conjugation of the substituent R with the carboxyl group in IV or V.
Shimizu
Kazuya
K
Graduate School of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan.
Takimoto
Masanori
M
Sato
Yoshihiro
Y
Mori
Miwako
M
D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D000478:Alkylation; D000480:Alkynes / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D013237:Stereoisomerism
D000475:Alkenes; D000480:Alkynes; D002245:Carbon Dioxide; D009532:Nickel