Arylation of gem-difluoroalkenes using a Pd/Cu Co-catalytic system that avoids β-fluoride elimination |
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| Authors: | Kedong Yuan Taisiia Feoktistova Paul Ha-Yeon Cheong Ryan A Altman |
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| Institution: | Tianjin Key Laboratory of Advanced Functional Porous Materials, Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384 P. R. China ; Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis OR USA.; Department of Medicinal Chemistry and Molecular Pharmacology, Department of Chemistry, Purdue University, West Lafayette IN 47907 USA, |
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| Abstract: | PdII/CuI co-catalyze an arylation reaction of gem-difluoroalkenes using arylsulfonyl chlorides to deliver α,α-difluorobenzyl products. The reaction proceeds through a β,β-difluoroalkyl–Pd intermediate that typically undergoes unimolecular β-F elimination to deliver monofluorinated alkene products in a net C–F functionalization reaction. However to avoid β-F elimination, we offer the β,β-difluoroalkyl–Pd intermediate an alternate low-energy route involving β-H elimination to ultimately deliver difluorinated products in a net arylation/isomerization sequence. Overall, this reaction enables exploration of new reactivities of unstable fluorinated alkyl–metal species, while also providing new opportunities for transforming readily available fluorinated alkenes into more elaborate substructures.PdII/CuI co-catalyze a desulfitative arylation of aliphatic gem-difluoroalkenes in a radical arylation/migratory insertion sequence that avoids β-F elimination. |
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