Anodic Olefin Coupling Reactions: Elucidating Radical Cation Mechanisms and the Interplay between Cyclization and Second Oxidation Steps

Anodic Olefin Coupling Reactions: Elucidating Radical Cation Mechanisms and the Interplay between Cyclization and Second Oxidation Steps
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阳极烯烃偶联反应:阐明自由基阳离子机制以及环化与第二氧化步骤之间的相互作用

DOI:
10.1002/tcr.202100118
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发表时间:
2021
期刊:
The Chemical Record
影响因子:
--
通讯作者:
Moeller, Kevin D.
Moeller, Kevin D.
中科院分区:
--
文献类型:
--
作者:
Medcalf, Zach;Moeller, Kevin D.

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阳极烯烃偶联反应通过净双电子过程产生新的键和环骨架,该过程反转已知的富电子官能团的极性。虽然这些反应机理的早期工作主要集中在该过程的初始氧化和环化步骤,但第二氧化步骤在决定反应成功方面也起着核心作用。支持这一观察结果的证据,沿着的证据表明,优化这第二个氧化步骤是不够的,拉一个差的环化所需的产品。成功的环化反应需要优化这两个过程。
Anodic olefin coupling reactions generate new bonds and ring skeletons through a net two electron process that reverses the polarity of a known, electron‐rich functional group. While much of the early work on the mechanism of these reactions focused on the initial oxidation and cyclization steps of the process, the second oxidation step also plays a central role in determining the success of the reaction. Evidence supporting this observation is presented, along with evidence that optimization of this second oxidation step is not enough to pull a poor cyclization to the desired product. Successful cyclization reactions require optimization of both processes.