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一类新型的有机催化剂:亚磺酸盐阴离子。

A new class of organocatalysts: sulfenate anions.

机构信息

Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania, 231 S. 34thSt., Philadelphia, PA 19104-6323 (USA) https://sites.google.com/site/titaniumupenn/

出版信息

Angew Chem Int Ed Engl. 2014 Sep 26;53(40):10755-8. doi: 10.1002/anie.201405996. Epub 2014 Aug 11.

Abstract

Sulfenate anions are known to act as highly reactive species in the organic arena. Now they premiere as organocatalysts. Proof of concept is offered by the sulfoxide/sulfenate-catalyzed (1-10 mol%) coupling of benzyl halides in the presence of base to generate trans-stilbenes in good to excellent yields (up to 99%). Mechanistic studies support the intermediacy of sulfenate anions, and the deprotonated sulfoxide was determined to be the resting state of the catalyst.

摘要

亚磺酸盐阴离子在有机领域被认为是具有高反应活性的物质。现在,它们首次作为有机催化剂出现。亚砜/亚磺酸盐催化(1-10 mol%)在碱存在下苄基卤化物偶联生成反式二苯乙烯的反应提供了概念验证,产率良好到优秀(高达 99%)。机理研究支持了亚磺酸盐阴离子的中间体性质,并且确定去质子化的亚砜是催化剂的休眠状态。

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