The Perfluorophenylation Of Aryl Chloride And Arylsulfonyl Halide

Fluorinated organic compounds increasingly gain importance in numerous areas of chemistry and everyday life.Building blocks which contain fluorinated entities are of high significance in areas such as materials science,catalysis,medicine,and biochemistry.This is because the reactivity and properties of molecules and ions can change dramatically in the presence of fluorinated moieties.Therefore,it is very meaningful to find a suitable method to introduce fluorine-containing groups into organic compounds,and obtaining organic fluo-rine compounds through nucleophilic fluorination is an effective method.Based on the previous reported,we study the synthesis methods of pentafluorophenylbi-phenyl derivatives,pentafluorophenylarylsulfide and pentafluorophenylarylsulfonyl com-pounds with triethoxypentafluorophenylsilane?C₆F₅-Si?OEt?₃?or trimethylpentafluoro-phenylsilane?C₆F₅-Si Me₃?as the source of perfluorophenyl group.This article will be dis-cussed from the following three points.1)We report a new method for synthesizing pentafluorophenylbiphenyl with aryl chlo-ride and triethoxysilylpentafluoro?C₆F₅Si?OEt?₃?as substrates.In this paper,the type of catalyst,the type of ligand and the types of additives were optimized.The optimal conditions were palladium acetate as catalyst,X-phos as ligand,silver oxide as additive and toluene as solvent.After that,we continued to discuss the universality of the reaction substrate under optimal conditions,and a series of pentafluorophenyl biaryl compounds with different sub-stituents were synthesized in 42%-99%yield,including electron-donating substituents,elec-tron-withdrawing substituents,aromatic heterocycles,and naphthalene rings.Combining with GC-MS analysis,NMR spectrum and a series of experiments,we pro-posed a feasible reaction mechanism of this reaction.2)We report a new method for the synthesis of pentafluorophenyl aryl sulfide com-pounds using triethoxysilyl pentafluorobenzene?C₆F₅Si?OEt?₃?and sublimation sulfur and aryl boric acid as substrate.We have screened reaction substrate ratio,the types of base,and catalyst in the reaction system.The optimal conditions currently selected are cuprous thiocy-anate as the catalyst,phen as the ligand,potassium fluoride as the base,and silver carbonate as oxidizing agent,DMF as a solvent,reacted at room temperature for 24 h,the target product pentafluorophenyl p-toluene sulfide can be obtained with a yield of 71%.We have carried out a part of the substrate expansion under this condition,and can obtain the target product with a good yield,and then we will continue to explore the universality of the substrate.Combining with GC-MS analysis,NMR spectrum and a series of experiments,we pro-posed a feasible reaction mechanism of this reaction.3)We conducted a series of explorations on the reaction of p-toluenesulfonyl halide with trimethylpentafluorophenylsilane?C₆F₅Si Me₃?.First,some alkalis and solvents were screened,but the target product was not obtained.Then we explored its reaction conditions under transition metal catalysis,screened the catalyst and ligand,and also failed to obtain the target product.In the next step,we plan to use other pentafluorophenyl reagents or pen-tafluorobenzene as the source of pentafluorobenzene,and continue to explore the synthesis method of pentafluorophenylarylsulfonyl compounds.