Kim Suji, Lee Sunwoo
Department of Chemistry, Chonnam National University, Gwangju, 61186 Republic of Korea.
Org Biomol Chem. 2024 Jun 5;22(22):4436-4444. doi: 10.1039/d4ob00215f.
An electrochemical synthetic method for the synthesis of sulfinic esters and sulfonic esters from sulfonyl hydrazides was developed. Alkyl sulfinic esters were synthesized by treating sulfonyl hydrazides with trialkyl orthoformate in a DMF solvent at a constant current of 5 mA and then optimizing the reaction conditions. Conversely, alkyl sulfonic esters were exclusively obtained when the reaction was conducted in alkyl alcohol solvents at a constant current of 15 mA. The various substituted arylsulfonyl hydrazides afforded moderate to good yields of the desired sulfinic esters and sulfonic esters. Mechanistic investigations revealed that sulfonyl radicals were formed through electrochemical oxidation and that they react with alkyl radicals or alkoxy radicals to generate the respective ester products.
开发了一种由磺酰肼合成亚磺酸酯和磺酸酯的电化学合成方法。通过在DMF溶剂中以5 mA的恒定电流用原甲酸三烷基酯处理磺酰肼，然后优化反应条件，合成了烷基亚磺酸酯。相反，当反应在烷基醇溶剂中以15 mA的恒定电流进行时，仅得到烷基磺酸酯。各种取代的芳基磺酰肼得到了所需亚磺酸酯和磺酸酯的中等至良好产率。机理研究表明，磺酰基自由基通过电化学氧化形成，并且它们与烷基自由基或烷氧基自由基反应生成相应的酯产物。
