Palladium-Catalyzed Intermolecular Trans-Selective Carbofunctionalization of Internal Alkynes to Highly Functionalized Alkenes,ACS Catalysis

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Palladium-Catalyzed Intermolecular Trans-Selective Carbofunctionalization of Internal Alkynes to Highly Functionalized Alkenes
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-08-24 , DOI: 10.1021/acscatal.0c02522
Weiwei Lv ₁ , Shihan Liu ₂ , Yanhui Chen ₁ , Si Wen ₁ , Yu Lan _{2,

3} , Guolin Cheng ₁

Affiliation

A palladium/DPEphos-catalyzed intermolecular trans-selective carbofunctionalization of internal alkynes has been established herein. This method proceeds through a formal anti-carbopalladation, forming trans-alkenyl palladium species, which was trapped by aryl boronic acids to provide all-carbon tetrasubstituted alkenes in 32–92% yields. The trans-selective arylsilylation/remote C–H silylation and hydroarylation/remote C–H borylation of internal alkynes were also achieved using hexamethyldisilane and bis(pinacolato)diboron as trapping reagents, respectively. The reaction features good regio- and stereoselectivity and high functional group tolerance. A preliminary mechanistic study and DFT calculations show that a cis to trans isomerization of cis-alkenyl palladium species was involved in this transformation.

中文翻译：

钯催化内部炔烃的分子间反选择碳官能化为高度官能化的烯烃

本文已经建立了内部炔烃的钯/ DPEphos催化的分子间反选择性碳官能化。该方法通过正式的抗碳链缩合反应，形成反式链烯基钯物质，被芳基硼酸捕获，以32-92％的产率提供全碳四取代烯烃。内部炔烃的反式芳基甲硅烷基化/远程CH甲硅烷基化和加氢芳基化/远程CH甲硼化也分别使用六甲基乙硅烷和双（频哪醇）二硼作为捕获剂实现。该反应具有良好的区域选择性和立体选择性以及高官能团耐受性。初步的机理研究和DFT计算表明，顺式为顺式异构化-烯基钯物质参与该转化。

更新日期：2020-09-20

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