Mn(OAc)3-Mediated Addition Reactions of NaSO2CF3 and Perhalogenated Carboxylic Acids with Unactivated Alkenes Conjectured by a Single Electron Transfer and Halogen Abstraction Mechanism

Hui Sun; Guannan Cui; Huijian Shang; Bin Cui

doi:10.1021/acs.joc.0c02086

Mn(OAc)₃-Mediated Addition Reactions of NaSO₂CF₃ and Perhalogenated Carboxylic Acids with Unactivated Alkenes Conjectured by a Single Electron Transfer and Halogen Abstraction Mechanism

J Org Chem. 2020 Dec 4;85(23):15241-15255. doi: 10.1021/acs.joc.0c02086. Epub 2020 Nov 17.

Authors

Hui Sun¹, Guannan Cui¹, Huijian Shang¹, Bin Cui¹

Affiliation

¹ College of Chemistry and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, People's Republic of China.

PMID: 33200607
DOI: 10.1021/acs.joc.0c02086

Abstract

A free-radical halotrifluoromethylation of olefins by using Mn(OAc)₃·2H₂O, CF₃SO₂Na, and perhalogenated carboxylic acids has been achieved. Perhalogenated carboxylic acids act as a halogen source and CF₃SO₂Na acts as a CF₃ source. The reaction displayed good tolerance of functional groups in the substrates under mild conditions. The radical clock experiment and TEMPO inhibition experiment support a radical process. The halogen reagent competition experiment shows that the last step of halogenation process is mainly through a halogen abstraction mechanism.