Catalytic Alkynylation of Polyfluoroarenes by Amide Base Generated In Situ

We herein demonstrate that the amide base generated in situ from CsF and N(TMS)₃ catalyzes the deprotonative coupling reactions of terminal alkynes with polyfluoroarenes, wherein mono- and dialkynylations occur efficiently for penta- and hexafluorobenzenes, respectively. Tetraalkynylated products could also be synthesized from dialkynylated compounds.     

Palladium‐catalyzed direct arylation of polyfluoroarene and facile synthesis of liquid crystal compounds

A convenient approach has been developed to prepare polyfluorobiphenyl by Pd(OAc)₂/PCy₃‐catalyzed direct arylation of polyfluoroarenes with aromatic halides in the presence of Cs₂CO₃ as base and toluene as solvent. In most cases, the desired arylated products of aromatic bromides were obtained in good to excellent yield at 80°C, and aryl chlorides also gave modest to good yields of arylated products at 110°C. According to this efficient C―C bondforming method, polyfluorobiphenyl liquid crystal compounds were prepared by Pd‐catalyzed direct arylation reactions of polyfluoroarenes with long alkyl chain substituted aryl bromides in 62–96% yield. Copyright © 2014 John Wiley & Sons, Ltd.     

Pd-catalyzed cross-coupling of polyfluoroarenes with cyclic vinyl triflates

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Generation of Polyfluoroaryl‐Fused H‐Pyrazolo[5,1‐a]isoquinolines through a Reaction of N′‐(2‐Alkynylbenzylidene)hydrazide with Polyfluoroarene

Polyfluoroarene reacts with N′‐(2‐alkynylbenzylidene)hydrazide catalyzed by silver triflate in the presence of cesium carbonate, leading to polyfluoroaryl‐fused H‐pyrazolo[5,1‐a]isoquinolines in good yields.     

Synthesis and biological activity of polyfluorinated p-aminosalicylic acids and their amides

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Copper-Catalyzed Defluorinative Hydroarylation of Alkenes with Polyfluoroarenes

A catalytic defluorinative hydroarylation of alkenes with polyfluoroarenes in the presence of dppbz-ligated Cu catalyst and silanes was developed. This method provides a straightforward and alternative avenue to synthetic important polyfluorinated arenes with readily available and bench-stable alkenes as latent nucleophiles, and therefore avoids conventional reliance on stoichiometric quantities of organometallic reagents. This reaction proceeds under very mild conditions and exhibits good functional group compatibility and high level of regioselectivity. The synthetic potential of this method was further demonstrated by a gram-scale synthesis, and an array of experimental studies were also carried out to elaborate the probable mechanism.