Development and Mechanistic Studies of (E)-Selective Isomerization/Tandem Hydroarylation Reactions of Alkenes with a Nickel(0)/Phosphine Catalyst
Development and Mechanistic Studies of (E)-Selective Isomerization/Tandem Hydroarylation Reactions of Alkenes with a Nickel(0)/Phosphine Catalyst
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DOI：
10.1021/acscatal.1c00908
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发表时间：
2021-05-26
期刊：
影响因子：
12.9
通讯作者：
Ogoshi, Sensuke
中科院分区：
文献类型：
--
作者：
Iwamoto, Hiroaki;Tsuruta, Takuya;Ogoshi, Sensuke
已经开发出使用镍（0）催化剂的立体选择性烯烃异构化和与芳基硼酸的连续加氢芳基化。大体积的单膦 PAd(2)(n-Bu) 是这些反应中的有效配体，可提供各种立体定义的内烯烃和加氢芳基化产物（异构化：高达 98%，E/Z = 98:2；串联加氢芳基化：高达 82%）。基于实验和计算计算的机理研究表明异构化是通过分子内或分子间氢位移进行的。此外，发现与硼酸辅助的烯烃氧化原金属化的协同多键重组是在加氢芳基化中由烯烃、镍(0)、醇和硼酸形成烷基镍(II)物质的合理机制。
A stereoselective alkene isomerization and sequential hydroarylation with arylboronic acid using a nickel(0) catalyst has been developed. The bulky monophosphine PAd(2)(n-Bu) is an effective ligand in these reactions to furnish both various stereo-defined internal alkenes and hydroarylation products (isomerization: up to 98%, E/Z = 98:2; tandem hydroarylation: up to 82%). Mechanistic studies based on experiments and computational calculations suggested that the isomerization proceeds via an intra- or intermolecular hydrogen shift. Furthermore, a concerted multibond recombination with boronic acid-assisted oxidative protometallation of the alkene was found to be a reasonable mechanism for the formation of the alkylnickel(II) species from the alkene, nickel(0), alcohol, and boronic acid in the hydroarylation.