Regioselective Single-Electron Tsuji-Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach.
Regioselective Single-Electron Tsuji-Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach.
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DOI：
10.1021/acs.orglett.9b02473
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发表时间：
2019-08
期刊：
影响因子：
5.2
通讯作者：
Zheng-Jun Wang;Shuai Zheng;Eugénie Romero;J. K. Matsui;G. Molander
中科院分区：
文献类型：
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作者：
Zheng-Jun Wang;Shuai Zheng;Eugénie Romero;J. K. Matsui;G. Molander
描述了通过光氧化还原/镍双重催化对烯丙醇衍生的伴侣与各种烷基 1,4-二氢吡啶进行自由基介导的官能化。这种转变以高线性和电子选择性发生，避免了恶劣条件的要求（例如强碱、高温）。另外，使用芳基亚磺酸盐作为自由基前体，也可以获得烯丙基砜。动力学同位素效应实验表明镍催化剂与烯丙基亲电子试剂的氧化加成是周转限制步骤，支持了之前的计算研究。
A radical-mediated functionalization of allyl alcohol derived partners with a variety of alkyl 1,4-dihydropyridines via photoredox/nickel dual catalysis is described. This transformation transpires with high linear and E-selectivity, avoiding the requirement of harsh conditions (e.g., strong base, elevated temperature). Additionally, using aryl sulfinate salts as radical precursors, allyl sulfones can also be obtained. Kinetic isotope effect experiments implicated oxidative addition of the nickel catalyst to the allylic electrophile as the turnover-limiting step, supporting previous computational studies.