1407162-96-2Relevant academic research and scientific papers
Utility of Organoboron Reagents in Arylation of Cyclopropanols via Chelated Pd(II) Catalysis: Chemoselective Access to β-Aryl Ketones
Ilangovan, Andivelu,Ramar, Thangeswaran,Subbaiah, Murugaiah A. M.
, (2020/07/03)
Organoborane reagents were investigated as coupling partners to cyclopropanol-derived β-ketone enolates in the presence of a chelated Pd(II) catalyst. Efficient coupling of a range of electronically and sterically diverse cyclopropanols and aryl/alkenyl boronic derivatives (39 examples, 65-94% yield) could be achieved with the generation of synthetically important β-aryl ketone intermediates in a chemoselective fashion. This reactivity paradigm, which broadens the scope of aryl donor partners to homoenolates, allows open-flask conditions, water as a cosolvent, and preparation of halogen-bearing β-aryl ketones that are distinct from previous methods. This chelated Pd(II) catalysis appears to be different from the Pd(0) pathway, as evident from deuterium scrambling studies that could reveal differentiating protonolysis of an α-keto carbopalladium complex in the terminal step.
Methanol as hydrogen source: Chemoselective transfer hydrogenation of α,β-unsaturated ketones with a rhodacycle
Aboo, Ahmed H.,Begum, Robina,Zhao, Liangliang,Farooqi, Zahoor H.,Xiao, Jianliang
, p. 1795 - 1799 (2019/11/11)
Methanol is a safe, economic and easy-to-handle hydrogen source. It has rarely been used in transfer hydrogenation reactions, however. We herein report that a cyclometalated rhodium complex, rhodacycle, catalyzes highly chemoselective hydrogenation of α,β-unsaturated ketones with methanol as the hydrogen source. A wide variety of chalcones, styryl methyl ketones and vinyl methyl ketones, including sterically demanding ones, were reduced to the saturated ketones in refluxing methanol in a short reaction time, with no need for inter gas protection, and no reduction of the carbonyl moieties was observed. The catalysis described provides a practically easy and operationally safe method for the reduction of olefinic bonds in α,β-unsaturated ketone compounds.
Catalyst-free dehydrative α-alkylation of ketones with alcohols: Green and selective autocatalyzed synthesis of alcohols and ketones
Xu, Qing,Chen, Jianhui,Tian, Haiwen,Yuan, Xueqin,Li, Shuangyan,Zhou, Chongkuan,Liu, Jianping
, p. 225 - 229 (2014/01/17)
Direct dehydrative α-alkylation reactions of ketones with alcohols are now realized under simple, practical, and green conditions without using external catalysts. These catalyst-free autocatalyzed alkylation methods can efficiently afford useful alkylated ketone or alcohol products in a one-pot manner and on a large scale by Ci￡C bond formation of the in situ generated intermediates with subsequent controllable and selective Meerwein-Pondorf-Verley-Oppenauer-type redox processes. Plain and simple: The title reaction has been realized under simple and practical conditions without using external catalysts, and can afford alkylated ketone or alcohol products in a one-pot manner and on a large scale. The reaction proceeds by Ci￡C bond formation of the in situ generated intermediates with subsequent controllable and selective Meerwein-Pondorf-Verley-Oppenauer-type redox processes. Copyright
Ligated regioselective PdII catalysis to access β-aryl-bearing aldehydes, ketones, and β-keto esters
Vellakkaran, Mari,Andappan, Murugaiah M. S.,Kommu, Nagaiah
supporting information; experimental part, p. 4694 - 4698 (2012/09/22)
By employing ligands in the PdII-mediated arylative isomerization of allyl alcohols, a milder and regioselective access to the versatile building blocks β-aryl aldehydes and ketones was developed. This new and chelation-controlled protocol enabled the compatibility of wide range of functionalities to generate dihydrochalcones, α-benzyl-α′- alkyl acetones, dihydrocinnamaldehydes, and α-benzyl β-keto esters (from Baylis-Hillman adducts). A practical multigram synthesis of an intermediate for Propafenone was also demonstrated. Copyright
