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钯催化酮与二芳基碘鎓盐的直接β-芳基化反应:一种无化学计量重金属且用户友好的方法。

Palladium-catalyzed direct β-arylation of ketones with diaryliodonium salts: a stoichiometric heavy metal-free and user-friendly approach.

作者信息

Huang Zhongxing, Sam Quynh P, Dong Guangbin

机构信息

The University of Texas at Austin , Department of Chemistry , Austin , TX 78712 , USA.

出版信息

Chem Sci. 2015 Oct 1;6(10):5491-5498. doi: 10.1039/c5sc01636c. Epub 2015 Jun 17.

Abstract

We herein report a new protocol for the Pd-catalyzed β-arylation of ketones without stoichiometric heavy metals. Widely accessible diaryliodonium salts are used as both the oxidant and aryl source. This tandem redox catalysis merges ketone dehydrogenation and conjugate addition without an additional oxidant or reductant. This transformation features the use of a unique bis--tosylsulfilimine ligand and the combination of potassium trifluoroacetate/trifluoroacetic acid to maintain an appropriate acidity of the reaction medium. The reaction tolerates both air and moisture, and shows a broad substrate scope. Kinetics studies, along with filtration and poisoning tests, support the involvement of palladium nanoparticles in the catalysis.

摘要

我们在此报告一种用于钯催化酮的β-芳基化反应的新方案,该方案无需化学计量的重金属。广泛可得的二芳基碘鎓盐用作氧化剂和芳基源。这种串联氧化还原催化将酮脱氢和共轭加成合并,无需额外的氧化剂或还原剂。该转化反应的特点是使用独特的双对甲苯磺酰基亚磺酰亚胺配体以及三氟乙酸钾/三氟乙酸的组合来维持反应介质的适当酸度。该反应耐受空气和湿气,并且底物范围广泛。动力学研究以及过滤和中毒测试支持钯纳米颗粒参与催化过程。

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