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新型缺电子膦基恶唑啉配体促进的钯催化无环酯类似物的α,β-脱氢反应

Palladium-catalyzed α,β-dehydrogenation of acyclic ester equivalents promoted by a novel electron deficient phosphinooxazoline ligand.

作者信息

Fulton Tyler J, Wu Brenda, Alexy Eric J, Zhang Haiming, Stoltz Brian M

机构信息

Warren and Katharine Schlinger Laboratory of Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd, Pasadena, California 91125, United States of America.

Small Molecule Process Chemistry, Genentech, Inc., 1 DNA Way, South San Francisco, California 94080, United States of America.

出版信息

Tetrahedron. 2019 Aug 2;75(31):4104-4109. doi: 10.1016/j.tet.2019.05.065. Epub 2019 Jun 1.

Abstract

A unique example of Pd-catalyzed decarboxylative dehydrogenation of fully substituted -acyl allyl enol carbonates is enabled by a new electron deficient phosphinooxazoline (PHOX) ligand. The reaction proceeds from the -enol carbonate to provide dehydrogenation products exclusively in high selectivity, while the -enol carbonate provides the α-allylation product with only minor dehydrogenation. The reaction proceeds with a broad scope of ()-enol carbonates derived from -acyl indoles to furnish acyclic formal α,β-unsaturated ester equivalents.

摘要

一种新型缺电子膦基恶唑啉(PHOX)配体实现了完全取代的α-酰基烯丙基烯醇碳酸酯的钯催化脱羧脱氢反应的独特实例。该反应从α-烯醇碳酸酯开始,以高选择性专一性地生成脱氢产物,而β-烯醇碳酸酯仅提供少量脱氢的α-烯丙基化产物。该反应适用于多种由α-酰基吲哚衍生的(α,β)-烯醇碳酸酯,以提供非环状的形式α,β-不饱和酯等价物。

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Palladium-Catalyzed α,β-Dehydrogenation of Esters and Nitriles.钯催化的酯和腈的α,β-脱氢反应。
J Am Chem Soc. 2015 May 13;137(18):5875-8. doi: 10.1021/jacs.5b02243. Epub 2015 Apr 28.

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