31480-67-8Relevant articles and documents
Scope and Mechanism of the Redox-Active 1,2-Benzoquinone Enabled Ruthenium-Catalyzed Deaminative α-Alkylation of Ketones with Amines
Kirinde Arachchige, Pandula T.,Handunneththige, Suhashini,Talipov, Marat R.,Kalutharage, Nishantha,Yi, Chae S.
, p. 13962 - 13972 (2021/11/20)
The catalytic system formed in situ from the reaction of a cationic Ru-H complex with 3,4,5,6-tetrachloro-1,2-benzoquinone was found to mediate a regioselective deaminative coupling reaction of ketones with amines to form the α-alkylated ketone products. Both benzylic and aliphatic primary amines were found to be suitable substrates for the coupling reaction with ketones in forming the α-alkylated ketone products. The coupling reaction of PhCOCD3 with 4-methoxybenzylamine showed an extensive H/D exchange on both α-CH2 (41% D) and β-CH2 (21%) positions on the alkylation product. The Hammett plot obtained from the reaction of acetophenone with para-substituted benzylamines p-X-C6H4CH2NH2 (X = OMe, Me, H, F, Cl, CF3) showed a strong promotional effect by the amine substrates with electron-releasing groups (ρ = -0.49 ± 0.1). The most significant carbon isotope effect was observed on the α-carbon of the alkylation product (Cα = 1.020) from the coupling reaction of acetophenone with 4-methoxybenzylamine. The kinetics of the alkylation reaction from an isolated imine substrate led to the empirical rate law: rate = k[Ru][imine]. A catalytically active Ru-catecholate complex was synthesized from the reaction of the cationic Ru-H complex with 3,5-di-tert-butyl-1,2-benzoquinone and PCy3. The DFT computational study was performed on the alkylation reaction, which revealed a stepwise mechanism of the [1,3]-carbon migration step via the formation of a Ru(IV)-alkyl species with a moderate energy of activation (ΔG? = 32-42 kcal/mol). A plausible mechanism of the catalytic alkylation reaction via an intramolecular [1,3]-alkyl migration of an Ru-enamine intermediate has been compiled on the basis of these experimental and computational data.
Ni-Catalyzed β-Alkylation of Cyclopropanol-Derived Homoenolates
Mills, L. Reginald,Zhou, Cuihan,Fung, Emily,Rousseaux, Sophie A. L.
supporting information, p. 8805 - 8809 (2019/11/03)
Metal homoenolates are valuable synthetic intermediates which provide access to β-functionalized ketones. In this report, we disclose a Ni-catalyzed β-alkylation reaction of cyclopropanol-derived homoenolates using redox-active N-hydroxyphthalimide (NHPI) esters as the alkylating reagents. The reaction is compatible with 1°, 2°, and 3° NHPI esters. Mechanistic studies imply radical activation of the NHPI ester and 2e β-carbon elimination occurring on the cyclopropanol.
TRISUBSTITUTED THIAZOLE COMPOUNDS, PREPARATIONS METHODS, PHARMACEUTICAL COMPOSITIONS AND MEDICALS USES THEREOF
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Page/Page column 30, (2009/12/23)
The present invention relates to 2,4,5-trisubstituted thiazole compounds of formula (I) or all possible isomers, prodrugs, pharmaceutically acceptable salts, solvates or hydrates thereof for the inhibition of plasma PLTP activity and/or plasma CETP activity, wherein the substituents are as defined in the specification; a process for the preparation of the compounds of formula (I); a pharmaceutical composition comprising the compound of formula (I) and its use for the preparation of a medicament for treatment and/or prevention of diseases associated with the increased plasma PLTP activity and/or the increased plasma CETP activity in a mammal, such as atherosclerosis, cardiovascular diseases and peripheral vascular diseases, etc.
