10326-99-5Relevant articles and documents
A Convenient Ruthenium-Catalysed α-Methylation of Carbonyl Compounds using Methanol
Dang, Tuan Thanh,Seayad, Abdul Majeed
, p. 3373 - 3380 (2016)
An efficient ruthenium catalyst is reported, for the first time, to catalyse the α-methylation of ketones and esters using methanol as a green methylating agent. The in situ generated catalyst from the complexes [RuCp*Cl2]2or [RuCp*Cl2]nwith dpePhos provided up to quantitative yields in the presence of only 20 mol% of lithium tert-butoxide (LiO-t-Bu) as a base. Regioselective mono- or multi-methylation could be effectively controlled by temperature. This catalyst system was also effective for the one-pot sequential α-alkylation–α-methylation of methyl ketones and conjugate reduction–α-methylation of α,β-unsaturated ketones to synthesise α-branched ketones. An application of the α-methylation of esters using the ruthenium catalyst was demonstrated for an alternative catalytic synthesis of Ketoprofen. (Figure presented.).
Palladium-catalyzed arylation of vinylic acetates. Phosphine ligand influenced regioselectivity
Jean, Micka?l,Renault, Jacques,Van De Weghe, Pierre
supporting information; experimental part, p. 6546 - 6548 (2011/02/23)
A palladium-catalyzed coupling reaction of aryl bromides with vinylic acetates in the presence of tributyltin methoxide h as been described. The α-arylation aldehyde product and the aryl ketone were obtained in the presence of P(t-Bu)3 and P(o-
Kinetics, Isotope Effects, and Mechanism of the Reaction of 1-Nitro-1-(4-nitrophenyl)alkanes with DBU in Acetonitrile
Galezowski, Wlodzimierz,Jarczewski, Arnold
, p. 1647 - 1656 (2007/10/02)
The kinetics of the reaction of O2NC6H4C(L)(R)NO2 (R = Me, Et, Pri, NNPE, NNPP, or MNNPP, respectively; L = H, D) with 1,8-diazabicycloundec-7-ene (DBU) in acetonitrile (MeCN) are reported.The nature of the product indicates that substantial dissociation into free ions occurs.The usefulness of Benesi-Hildebrand relationship for distinguishing between ion pairs and ions of the product is discussed in detail.The reaction shows low activation enthalpy value ΔH(excit.) = 15.4, 17.8, and 19.9 kJ mol-1 and large negative entropies of activation ΔS(excit.) = -131, -134, and -147 J mol-1 K-1 for NNPE, NNPP, and MNNPP respectively.The kinetic isotope effects kH/kD (12.5, 12.4, and 12.3) are large, showing no variation, the more sterically hindered the substrate.The values of the isotope effects exerted on the activation parameters indicate the contribution of a tunnelling effect QH/QD = 1.35 at 25 deg C.The influence of water on the kinetics is also examined and discussed with respect to reliability of kinetic measurements of such reactions systems.