90819-57-1Relevant articles and documents
Nickel-Catalyzed Cyanation of Aryl Thioethers
Delcaillau, Tristan,Woenckhaus-Alvarez, Adrian,Morandi, Bill
, p. 7018 - 7022 (2021/09/13)
A nickel-catalyzed cyanation of aryl thioethers using Zn(CN)2 as a cyanide source has been developed to access functionalized aryl nitriles. The ligand dcype (1,2-bis(dicyclohexylphosphino)ethane) in combination with the base KOAc (potassium acetate) is essential for achieving this transformation efficiently. This reaction involves both a C-S bond activation and a C-C bond formation. The scalability, low catalyst and reagents loadings, and high functional group tolerance have enabled both late-stage derivatization and polymer recycling, demonstrating the reaction's utility across organic chemistry.
Palladium-catalyzed synthesis of aryl ketones by coupling of aryl bromides with an acyl anion equivalent
Takemiya, Akihiro,Hartwig, John F.
, p. 14800 - 14801 (2008/02/05)
Palladium-catalyzed couplings of aryl bromides with N-tert-butylhydrazones as acyl anion equivalents to form aryl ketones are reported. The coupling process occurs at the C-position of hydrazones to form N-tert-butyl azo compounds. Isomerization of these azo compounds to the corresponding hydrazones, followed by hydrolysis, gave the desired mixed alkyl aryl ketones. The selectivity of C- versus N-arylation was strongly influenced by the substituent on nitrogen. Arylation at carbon occurred with N-tert-butylhydrazones, whereas N-arylation occurred with N-arylhydrazones. The arylation of hydrazones containing primary and secondary alkyl groups, as well as aryl groups, gave the desired ketones in good yields after hydrolysis. Functional groups on the aromatic ring, such as alkoxy, cyano, trifluoromethyl, carboalkoxy, carbamoyl, and keto groups, were tolerated. This reaction likely occurs by C-C bond-forming reductive elimination from an intermediate containing an η1-diazaallyl ligand. Copyright
Palladium-catalyzed acyldemetallation and carbonylation reactions of organomercurials for the synthesis of unsymmetrical ketones
Bumagin, N. A.,More, P. G.,Beletskaya, I. P.
, p. 379 - 388 (2007/10/02)
The palladium-catalyzed acyldemetallation reactions of organomercurials (R2Hg or AlkHgI) provide a mild, selective and general method for the synthesis of unsymmetrical heterocyclic ketones.High yields of ketones (RCOR') were obtained along with small amounts of homocoupling products (R2).The reaction is accelerated by a nucleophilic catalyst with both organic groups of R2Hg taking part in the reaction.The selectivity of the reaction towards the ketone can be increased by carrying out the reaction with a suitable combination of reactants under vacuum.The palladium-catalyzed carbonylation of organomercurials in the presence of ArI is another route to unsymmetrical ketones.The AlkHgI-ArI system undergoes carbonylation in the presence of palladium complex and excess iodide ion under mild conditions to give high yields of unsymmetrical ketones.The selectivity and rate of the reaction depend upon the nature of the catalyst, solvent and the concentration of iodide ion.