Using a Combination of Electrochemical and Photoelectron Transfer Reactions to Gain New Insights into Oxidative Cyclization Reactions
Using a Combination of Electrochemical and Photoelectron Transfer Reactions to Gain New Insights into Oxidative Cyclization Reactions
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DOI：
10.1149/1945-7111/abbe5c
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发表时间：
2020-10
影响因子：
3.9
通讯作者：
Matthew D. Graaf;Luisalberto Gonzalez;Zachary Medcalf;K. Moeller
中科院分区：
文献类型：
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作者：
Matthew D. Graaf;Luisalberto Gonzalez;Zachary Medcalf;K. Moeller
使用电化学或可见光和光氧化还原催化剂，富电子烯烃的一个电子氧化可以引发自由基阳离子引发的环化反应。原则上，这两种方法可用于提供互补的产物，其中电解导致衍生自净双电子氧化的产物，而光电子转移方法与来自氧化还原中性过程的产物的形成相容。然而，我们发现越来越多的氧化环化反应需要快速去除第二个电子，以形成高产率的所需产物。在这些情况下，电化学方法可以提供一种上级方法来获得必要的双电子氧化途径。也就是说，这两种方法的结合提供了理解反应何时具有这种要求所需的机理见解，并且我们发现，光氧化还原催化与电化学方法结合使用正在改变我们对迄今为止最成功的阳极环化反应的理解。
Radical cation initiated cyclization reactions can be triggered by the one electron oxidation of an electron-rich olefin using either electrochemistry or visible light and a photoredox catalyst. In principle, the two methods can be used to give complimentary products with the electrolysis leading to products derived from a net two electron oxidation and the photoelectron transfer method being compatible with the formation of products from a redox neutral process. However, we are finding an increasing number of oxidative cyclization reactions that require the rapid removal of a second electron in order to form high yields of the desired product. In those cases, the electrochemical method can provide a superior approach to accessing the necessary two electron oxidation pathway. With that said, it is a combination of the two methods that provides the mechanistic insight needed to understand when a reaction has this requirement, and we are finding that the use of photoredox catalysis in combination with electrochemical methods is changing our understanding of even the most successful anodic cyclization reactions run to date.