Hydrotrifluoromethylthiolation of Unactivated Alkenes and Alkynes with Trifluoromethanesulfonic Anhydride through Deoxygenative Reduction and Photoredox Radical Processes
Yao Ouyang
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Science, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032 China
Search for more papers by this authorDr. Xiu-Hua Xu
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Science, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Feng-Ling Qing
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Science, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032 China
Key Laboratory of Science and Technology of Eco-Textiles, Ministry of Education, College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, 2999 North Renmin Lu, Shanghai, 201620 China
Search for more papers by this authorYao Ouyang
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Science, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032 China
Search for more papers by this authorDr. Xiu-Hua Xu
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Science, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Feng-Ling Qing
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Science, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032 China
Key Laboratory of Science and Technology of Eco-Textiles, Ministry of Education, College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, 2999 North Renmin Lu, Shanghai, 201620 China
Search for more papers by this authorGraphical Abstract
A practical anti-Markovnikov hydrotrifluoromethylthiolation of unactivated alkenes using (CF3SO2)2O and H2O as the SCF3 and H sources was achieved through deoxygenative reduction with PMePh2 and photoredox radical processes. This reaction is the first example of using (CF3SO2)2O as a trifluoromethylthiolating reagent and provides a new strategy for radical trifluoromethylthiolation.
Abstract
An ongoing challenge in trifluoromethylthiolation reactions is the use of less expensive and easily available trifluoromethylthio sources. Herein, we disclose an unprecedented usage of trifluoromethanesulfonic anhydride (Tf2O) as a radical trifluoromethylthiolating reagent. Hydrotrifluoromethylthiolation of unactivated alkenes and alkynes with Tf2O in the presence of PMePh2 and H2O under visible-light photoredox catalysis gave the addition products. The trifluoromethylthio radical (.SCF3) was first formed from Tf2O through a photoredox radical processes and deoxygenative reduction of PMePh2, and H2O serves as the H-atom donor for the hydrotrifluoromethylthiolation reaction. This reaction provides a new strategy for radical trifluoromethylthiolation.
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