Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C-S Bond Cleavage: Reaction Development and Mechanism Study

Bingnan Du; Wenmin Wang; Yang Wang; Zhenghang Qi; Jiaqi Tian; Jie Zhou; Xiaochen Wang; Jianlin Han; Jing Ma; Yi Pan

doi:10.1002/asia.201701694

Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C-S Bond Cleavage: Reaction Development and Mechanism Study

Chem Asian J. 2018 Feb 16;13(4):404-408. doi: 10.1002/asia.201701694. Epub 2018 Feb 1.

Authors

Bingnan Du¹, Wenmin Wang², Yang Wang¹, Zhenghang Qi², Jiaqi Tian², Jie Zhou³, Xiaochen Wang¹, Jianlin Han¹, Jing Ma², Yi Pan¹

Affiliations

¹ School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, 210023, P. R. China.
² School of Chemistry and Chemical Engineering, Institute of Theoretical and Computational Chemistry, Nanjing University, Nanjing, 210023, P. R. China.
³ Shenzhen Research Institute of Nanjing University, Shenzhen, 518057, China.

PMID: 29328548
DOI: 10.1002/asia.201701694

Abstract

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^II 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.

Keywords: C-S bond cleavage; aerobic oxidation; copper; density fuctional calculations; β-keto sulfones.