Dual Oxidation of Epoxides with a High-Valent Cu(III)-CF3 Compound and DMSO to Access 1,2-Diketones

Dou-Dou Chen; Song-Lin Zhang

doi:10.1021/acs.joc.3c01160

Dual Oxidation of Epoxides with a High-Valent Cu(III)-CF₃ Compound and DMSO to Access 1,2-Diketones

J Org Chem. 2023 Dec 15;88(24):16735-16741. doi: 10.1021/acs.joc.3c01160. Epub 2023 Dec 5.

Authors

Dou-Dou Chen¹, Song-Lin Zhang¹

Affiliation

¹ Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, Jiangsu 214122, China.

PMID: 38050841
DOI: 10.1021/acs.joc.3c01160

Abstract

This study reports sequential dehydrogenation and transfer oxygenation of 1,2-diarylepoxides by high-valent phenCu(III)(CF₃)₃ and DMSO to produce 1,2-diketones. The Cu(III)-CF₃ compound serves as a CF₃ radical source to abstract the hydrogen atom of the epoxide ring. The resulting ether α-carbon radical undergoes ring-opening rearrangement to give a ketone α-carbon radical intermediate, which is oxygenated by DMSO with the release of Me₂S. The combination of a Cu(III)-CF₃ compound and DMSO may be exploited to develop other novel oxidation reactions.