16424-52-5Relevant articles and documents
Vinylboron Self-Promoted Carbonylative Coupling with Cyclobutanone Oxime Esters
Yin, Zhiping,Rabeah, Jabor,Brückner, Angelika,Wu, Xiao-Feng
, (2019)
Despite the significant progress that has been made in the area of catalyst-dependent chemistry, the exploration of a greener and more environmentally benign catalyst-free reaction remains one of the most important areas in modern chemistry. Herein, we present a vinylboron self-promoted carbonylative coupling with cyclobutanone oxime esters. Various cyclobutanone oxime esters and substituted styrylboronic acids can be transformed into the corresponding enones in moderate to good yields. Detailed EPR investigations and control experiments provide sufficient evidence to show that this reaction goes through a single-electron transfer process.
Synthetic method for preparing gamma-cyano substituted olefin by decarboxylation at room temperature
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Paragraph 0042-0045, (2021/04/07)
The invention provides a synthetic method for preparing gamma-cyano substituted olefin by decarboxylation at room temperature, and the method comprises the following steps: reacting unsaturated carboxylic acid and cyclic ketoxime ester in a solvent at room temperature under the promotion of nickel and ruthenium catalysts, ligand and illumination according to the following reaction formula to obtain gamma-cyano substituted olefin. According to the invention, the reaction of unsaturated carboxylic acid and cyclic ketoxime ester under mild conditions is realized for the first time. The method for decarboxylation synthesis of gamma-cyanoolefin has the advantages of mild reaction conditions, convenient operation, excellent functional group compatibility and high reaction yield. Cyano is an important organic structure fragment and widely exists in natural active products and drug molecules. The invention provides a mild, efficient and convenient synthesis method for olefin containing gamma cyano.
Tuning the Selectivity of Palladium Catalysts for Hydroformylation and Semihydrogenation of Alkynes: Experimental and Mechanistic Studies
Beller, Matthias,Ge, Yao,Jackstell, Ralf,Jiao, Haijun,Liu, Jiawang,Wei, Duo,Wei, Zhihong,Yang, Ji
, p. 12167 - 12181 (2020/11/27)
Here, we describe a selective palladium catalyst system for chemodivergent functionalization of alkynes with syngas. In the presence of an advanced ligand L2 bearing 2-pyridyl substituent as a built-in base, either hydroformylation or semihydrogenation of diverse alkynes occurs with high chemo- and stereoselectivity under comparable conditions. Mechanistic studies, including density functional theory (DFT) calculations, kinetic analysis, and control experiments, revealed that the strength and concentration of acidic cocatalysts play a decisive role in controlling the chemoselectivity. DFT studies disclosed that ligand L2 not only promotes heterolytic activation of hydrogen similar to frustrated Lewis pair (FLP) systems in the hydrogenolysis step for hydroformylation but also suppresses CO coordination to promote semihydrogenation under strong acid conditions. This switchable selectivity provides a strategy to design new catalysts for desired products.
