Selective Electrochemical Oxidation of Benzylic C–H to Benzylic Alcohols with the Aid of Imidazolium Radical Mediators,Journal of the American Chemical Society

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Selective Electrochemical Oxidation of Benzylic C–H to Benzylic Alcohols with the Aid of Imidazolium Radical Mediators
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-10-27 , DOI: 10.1021/jacs.3c09907
Fangfang Peng ₁ , Junfeng Xiang _{1,

2} , Huisheng Qin _{1,

2} , Bingfeng Chen ₁ , Ran Duan ₃ , Wenling Zhao ₁ , Shiqiang Liu ₁ , Tianbin Wu ₁ , Wenli Yuan ₁ , Qian Li ₁ , Jikun Li _{2,

3} , Xinchen Kang _{1,

2} , Buxing Han _{1,

2,

4}

Affiliation

Selective oxidation of benzylic C–H to benzylic alcohols is a well-known challenge in the chemical community since benzylic C–H is more prone to be overoxidized to benzylic ketones. In this work, we report the highly selective electro-oxidation of benzylic C–H to benzylic alcohols in an undivided cell in ionic liquid-based solution. As an example, the selectivity toward xanthydrol could be as high as 95.7% at complete conversion of xanthene, a typical benzylic C–H compound, on gram-scale in imidazolium bromide/H₂O/DMF. Mechanism investigation reveals that the imidazolium radical generated in situ participants in a proton-coupled electron transfer process and low-barrier hydrogen bonds stabilize the reaction intermediates, together steering the redox equilibrium, favoring benzylic alcohols over benzylic ketones.

中文翻译：

咪唑鎓自由基介体选择性电化学氧化苯甲基 C–H 生成苯甲醇

苄基 C-H 选择性氧化为苄基醇是化学界众所周知的挑战，因为苄基 C-H 更容易被过度氧化为苄基酮。在这项工作中，我们报告了在离子液体溶液中的未分割电池中，苄基 C–H 高度选择性电氧化为苄醇。_{例如，在溴化咪唑鎓/H 2} O/DMF中，克级的呫吨（一种典型的苄基 C-H 化合物）完全转化时，对呫吨醇的选择性可高达 95.7% 。机理研究表明，原位产生的咪唑自由基参与了质子耦合电子转移过程，并且低势垒氢键稳定了反应中间体，共同控制了氧化还原平衡，有利于苄醇而不是苄酮。

更新日期：2023-10-27

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