New insight into Cu-catalyzed borocarbonylative coupling reactions of alkenes with alkyl halides
New insight into Cu-catalyzed borocarbonylative coupling reactions of alkenes with alkyl halides
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DOI：
10.1016/j.jcat.2023.01.014
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发表时间：
2023-01
影响因子：
7.3
通讯作者：
Yanhong Liu;Aili Feng;Rongxiu Zhu;Chengbu Liu;Dongju Zhang
中科院分区：
文献类型：
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作者：
Yanhong Liu;Aili Feng;Rongxiu Zhu;Chengbu Liu;Dongju Zhang
密度泛函理论（DFT）计算是为了更好地理解最近文献报道的在 CO 气氛下使用双（频哪醇）二硼作为硼试剂，铜催化烯烃与卤代烷的四组分硼羰基化偶联的机理。一种意想不到的反应机制被证明是可行的，它是通过仅涉及 CuI、双配体中继、无自由基参与的铜催化以及 SN2 型 C 单键 C 偶联方式发生的。理论结果合理化了实验观察到的区域选择性和化学选择性以及烯烃的取代基效应以及自由基捕获剂完全抑制反应的事实。
Density functional theory (DFT) calculations were performed to better understand the mechanism of copper-catalyzed four-component borocarbonylative coupling of alkenes with alkyl halides by using bis(pinacolato)diboron as the boron reagent under CO atmosphere as reported in the recent literature. An unexpected reaction mechanism was shown to be viable, which occurs via a CuI-only involved, two-ligand relay-enabled, and no radical-participated copper catalysis with a SN2-type Csingle bondC coupling fashion. The theoretical results rationalized the experimentally observed regio- and chemoselectivities, and substituent effect of alkenes as well as the fact the reaction is totally inhibited by radical trapping reagents.