Jones Alan M
School of Pharmacy, University of Birmingham Edgbaston, Birmingham, B15 2TT, United Kingdom.
Chem Rec. 2021 Sep;21(9):2120-2129. doi: 10.1002/tcr.202000116. Epub 2020 Nov 4.
This Personal Account describes the author's groups' research in the field of electrosynthetic anodic oxidation, beginning with initial trial and error attempts with the Shono oxidation. Early setbacks with complex rotameric amide mixtures, provided the ideal environment for the discovery of the Oxa-Shono reaction-O -C bond cleavage of esters-providing two useful products in one-step: aldehyde selective oxidation level products and a mild de-esterification method to afford carboxylic acids in the process. The development of the Oxa-Shono reaction provided the impetus for the discovery of other electrically propelled-N -C and N -C -bond breaking reactions in bioactive amide and sulfonamide systems. Understanding the voltammetric behaviour of the molecule under study, switching between controlled current- or controlled potential- electrolysis, and restricting electron flow (the reagent), affords exquisite control over the reaction outcomes in batch and flow. Importantly, this bio-inspired advance in electrosynthetic dealkylation chemistry mimics the metabolic outcomes observed in nature.
这篇个人述评描述了作者团队在电合成阳极氧化领域的研究，始于对Shono氧化的初步反复试验。复杂旋转异构体酰胺混合物早期的挫折，为发现氧杂-Shono反应——酯的O-C键裂解——提供了理想环境，该反应能一步生成两种有用产物：醛选择性氧化水平产物以及在此过程中温和脱酯生成羧酸的方法。氧杂-Shono反应的发展为在生物活性酰胺和磺酰胺体系中发现其他电驱动的N-C和N-C键断裂反应提供了动力。了解所研究分子的伏安行为、在恒流或恒电位电解之间切换以及限制电子流动（试剂），能对间歇式和连续流反应结果进行精确控制。重要的是，这种电合成脱烷基化学领域受生物启发的进展模仿了自然界中观察到的代谢结果。
