Arylation of gem-difluoroalkenes using a Pd/Cu Co-catalytic system that avoids β-fluoride elimination. Issue 4 (8th December 2020)

• Record Type: Journal Article
• Authors: Yuan, Kedong; Feoktistova, Taisiia; Cheong, Paul Ha-Yeon; Altman, Ryan A.
• Is Part Of: Chemical science. Volume 12:Issue 4(2021)
• Page Start: 1363
• Page End: 1367
• Publication Date: 2020-12-08
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d0sc05192f
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Pd II /Cu I co-catalyze a desulfitative arylation of aliphatic gem -difluoroalkenes in a radical arylation/migratory insertion sequence that avoids β-F elimination. Abstract : Pd II /Cu I 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.