A copper catalytic system was established for the stereoselective hydrodefluorination of gem-difluoroalkenes through C-F activation to synthesize various Z fluoroalkenes. H O is used as the hydrogen source for the fluorine acceptor moiety. This mild catalytic system shows good-functional group compatibility, accepting a range of carbonyls as precursors to the gem-difluoroalkenes, including aliphatic, aromatic, and α,β-unsaturated aldehydes and even ketones. It serves as a powerful synthetic method for the late-stage modification of complex compounds.
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http://dx.doi.org/10.1002/anie.201708224 | DOI Listing |
Nat Commun
August 2024
School of Food and Biological Engineering, Hefei University of Technology, Hefei, China.
CF-containing compounds hold significant potential in drug discovery, organic synthesis, and materials science. However, synthesizing various CF-containing building blocks from a single compound remains challenging. Here, we present a Cu-catalyzed, switchable defluoroborylation and hydrodefluorination of trifluoromethylated alkynes, yielding four types of CF-containing compounds.
View Article and Find Full Text PDFChem Commun (Camb)
June 2024
College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, P. R. China.
The synthesis of deuterated -difluoroalkenes selective deuterodefluorination of β-CF-cinnamates using a nickel catalyst has been reported for the first time. Commercially available deuterated formic acid is a cheap and convenient deuterium source. The nickel-catalyst showed high selectivity for monodefluorination and avoided competitive reactions such as multiple defluorination or hydrogenation.
View Article and Find Full Text PDFOrg Lett
March 2024
School of Chemistry, Engineering Research Center of Energy Storage Materials and Devices, Ministry of Education, Xi'an Key Laboratory of Sustainable Energy Material Chemistry, Xi'an Jiaotong University, Xi'an, Shaanxi 710049, People's Republic of China.
We report a simple and economical method to synthesize monofluoroalkenes via the electrochemical hydrodefluorination of -difluoroalkenes. This reaction proceeds efficiently at room temperature, eliminating the requirement for a costly transition metal catalyst, ligand, and external reducing agent. The monofluoroalkene products can be obtained in medium to good yields and up to 99:1 / selectivity.
View Article and Find Full Text PDFOrg Lett
April 2023
Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China.
A concise and efficient hydrodefluorination process was developed for the synthesis of -difluoroalkenes. This reaction employs rongalite as a masked proton source and does not require any additional catalysts or reductants. Notably, trifluoromethyl alkenes having both terminal and internal double bonds are compatible with this process, allowing for a wider range of substrates.
View Article and Find Full Text PDFJ Org Chem
September 2021
Département de Chimie, Université Laval, 1045 avenue de la Médecine, Québec QC G1V 0A6, Canada.
An efficient route for the synthesis of 1-aryl-2,2-difluoroalkenes via 1,2-desilylative defluorination is disclosed. Only a catalytic amount of fluoride source is required to initiate the desilylation and afford -difluoroalkenes in very good to quantitative yields, using mild reaction conditions in dimethyl carbonate as a green solvent. This reaction uses (1-aryl)-2,2,2-trifluoroethyl-silanes, which are easily prepared via the insertion reaction of trifluoroethyl diazo alkanes into the Si-H bond of tertiary organosilanes.
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