76584-02-6Relevant academic research and scientific papers
Palladium-catalyzed reaction of γ-silylated allyl acetates proceeding through 1,2-shift of a substituent on silicon
Horino, Yoshikazu,Ishibashi, Mayo,Nakasai, Kosuke,Korenaga, Toshinobu
, (2020/08/28)
The palladium-catalyzed reaction of γ-silylated allyl acetates with water in the presence of CsF induces a previously unprecedented 1,2-shift of a substituent on silicon to produce allylsilanes in situ. The catalytic activity of the palladium increased when using an electron-poor phosphine ligand possessing fluorinated substituents. Further investigation of the reaction revealed that the approximate order of the migratory aptitude of groups from silicon was PhC≡C, allyl > Bn > Ph, vinyl > alkyl (Me, Et). A density functional theory study was employed to explore the reaction mechanism. Finally, the Hosomi–Sakurai-type allylation of aldehydes with in situ-generated α,γ-disubstituted allylsilanes was also investigated.
Nickel-Catalyzed Direct Coupling of Allylic Alcohols with Organoboron Reagents
Wang, Gaonan,Gan, Yi,Liu, Yuanhong
, p. 916 - 920 (2018/09/22)
The direct coupling of allylic alcohols with arylboronic acids or their derivatives catalyzed by Ni(cod)2 in the presence of a catalytic amount of base has been developed. A wide variety of allylic substrates or arylboronic acids turned out to be applicable to this catalytic system. The present method does not require the use of ligands for stabilizing the nickel catalyst in most cases or additional activators for activation of allylic alcohols.
tert-Butoxy and 2-furyl. Two effective substituents at stabilizing carbon-carbon double bonds
Hine, Jack,Linden, Shwn-Meei
, p. 1635 - 1638 (2007/10/02)
Potassium tert-butoxide was used as a catalyst at 25°C to establish equilibrium, approached from both sides, in two reactions of the type trans-PhCH = CHCH2X ? trans-PhCH2CH = CHX. At equilibrium in 80% dimethyl sulfoxide-20% tert-butyl alcohol, 4.3% trans-cinnamyl tert-butyl ether, 28.5% trans-3-phenyl-1-propenyl tert-butyl ether, and 67.2% cis-3-phenyl-1-propenyl tert-butyl ether were present. In tert-butyl alcohol, 22.4% trans-3-(2-furyl)-1-phenyl-1-propene, 72.8% trans-1-(2-furyl)-3-phenyl-1-propene, and 4.86% cis-1-(2-furyl)-3-phenyl-1-propene were present at equilibrium. These plus earlier observations show that the "double bond stabilizing abilityquot; of the tert-butoxy group is greater than that of the methoxy group and that the double bond stabilizing ability of the 2-furyl group is greater than that of the phenyl group. Reasons for these differences are discussed. In both cases steric factors are thought to be important.
