Du Bingnan, Wang Wenmin, Wang Yang, Qi Zhenghang, Tian Jiaqi, Zhou Jie, Wang Xiaochen, Han Jianlin, Ma Jing, Pan Yi
School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, 210023, P. R. China.
School of Chemistry and Chemical Engineering, Institute of Theoretical and Computational Chemistry, Nanjing University, Nanjing, 210023, P. R. China.
Chem Asian J. 2018 Feb 16;13(4):404-408. doi: 10.1002/asia.201701694. Epub 2018 Feb 1.
A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C-S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four-coordinated Cu intermediate, O-O bond homolysis induced C-S bond cleavage and Cu-catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C-S bond cleavage and transformations.
以氧气作为氧化剂，实现了铜催化的β-酮砜与醇的串联氧化自由基反应。在该反应中，β-酮砜在氧化条件下通过C-S键的断裂转化为亚磺酸酯。实验和计算研究表明，该反应涉及一条新的途径，该途径通过关键的四配位铜中间体的形成、O-O键均裂诱导的C-S键断裂以及铜催化的酯化反应来形成最终产物。该反应为磺酸酯提供了一种新策略，并丰富了C-S键断裂和转化的研究内容。
