We have developed a novel and straightforward protocol that facilitates the transformation of alkenylsulfonium salts leading to the direct synthesis of -difluoromethylated alkenes. The success of this method relies on the use of copper catalysis and Vicic-Mikami reagent (DMPU)Zn(CFH). These mild protocols offer the advantage of selectively synthesizing either aromatic or aliphatic difluoromethylated alkenes. Furthermore, our methodology extends to the perfluoroalkylation of alkenylsulfonium salts. Notably, this approach is conducive to large-scale synthesis and holds promise for diverse applications.
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http://dx.doi.org/10.1021/acs.orglett.4c04250 | DOI Listing |
Org Lett
December 2024
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, Jiangxi 330031, China.
Angew Chem Int Ed Engl
December 2022
College of Materials, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, Hangzhou, 311121, P. R. China.
A ligand-controlled rhodium-catalyzed regiodivergent arylation of alkenylthianthrenium salts with arylboroxines which allows the synthesis of terminal and internal alkene products in a switchable manner is reported. The use of a diene ligand guides the reaction toward cine-arylation affording terminal alkenes, while the use of a phosphine ligand switches the reaction to ipso-arylation exclusively giving internal alkenes. Deuterium labelling studies and DFT computations were carried out to investigate the mechanism.
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