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Manganese-Mediated Electrochemical Oxidation of Thioethers to Sulfoxides Using Water as the Source of Oxygen Atoms
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-07-23 , DOI: 10.1021/jacs.4c07058 Md Asmaul Hoque 1 , Tianxiao Jiang 1 , Darren L Poole 2 , Shannon S Stahl 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-07-23 , DOI: 10.1021/jacs.4c07058 Md Asmaul Hoque 1 , Tianxiao Jiang 1 , Darren L Poole 2 , Shannon S Stahl 1
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Oxygen-atom transfer reactions are a prominent class of synthetic redox reactions that often use high-energy oxygen-atom donor reagents. Electrochemical methods can bypass these reagents by using water as the source of oxygen atoms through pathways involving direct or indirect (mediated) electrolysis. Here, manganese porphyrins and related mediators are shown to be effective molecular electrocatalysts for selective oxidation of thioethers to sulfoxides, without overoxidation to the sulfone. The reactions proceed by proton-coupled oxidation of a MnIII–OH2 species to generate a MnIV–OH and MnV═O species. This methodology is compared to direct electrolysis methods initiated by single-electron oxidation of the thioether, and chloride-mediated electrochemical oxidation of thioethers. The Mn-mediated reactions operate at lower applied potential and exhibit improved substrate scope and functional group compatibility relative to direct electrolysis, and the tunability of the Mn-based mediators allows for improved performance relative to chloride-mediated electrolysis. An electrochemical parallel screening platform is developed and applied to a library of pharmaceutically relevant thioethers.
中文翻译：
以水作为氧原子源，锰介导的硫醚电化学氧化为亚砜
氧原子转移反应是一类重要的合成氧化还原反应，通常使用高能氧原子供体试剂。电化学方法可以通过涉及直接或间接（介导）电解的途径使用水作为氧原子源，从而绕过这些试剂。在这里，锰卟啉和相关介体被证明是有效的分子电催化剂，可将硫醚选择性氧化为亚砜，而不会过度氧化为砜。该反应通过 Mn III –OH 2物质的质子耦合氧化生成 Mn IV –OH 和 Mn V =O 物质。该方法与由硫醚的单电子氧化引发的直接电解方法和氯介导的硫醚电化学氧化进行比较。锰介导的反应在较低的施加电位下进行，并且相对于直接电解表现出改进的底物范围和官能团兼容性，并且锰基介体的可调性允许相对于氯化物介导的电解改进性能。开发了电化学平行筛选平台并将其应用于药学相关硫醚库。
更新日期：2024-07-23
中文翻译：
以水作为氧原子源，锰介导的硫醚电化学氧化为亚砜
氧原子转移反应是一类重要的合成氧化还原反应，通常使用高能氧原子供体试剂。电化学方法可以通过涉及直接或间接（介导）电解的途径使用水作为氧原子源，从而绕过这些试剂。在这里，锰卟啉和相关介体被证明是有效的分子电催化剂，可将硫醚选择性氧化为亚砜，而不会过度氧化为砜。该反应通过 Mn III –OH 2物质的质子耦合氧化生成 Mn IV –OH 和 Mn V =O 物质。该方法与由硫醚的单电子氧化引发的直接电解方法和氯介导的硫醚电化学氧化进行比较。锰介导的反应在较低的施加电位下进行，并且相对于直接电解表现出改进的底物范围和官能团兼容性，并且锰基介体的可调性允许相对于氯化物介导的电解改进性能。开发了电化学平行筛选平台并将其应用于药学相关硫醚库。
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