Palladium-Catalyzed Cross-Coupling Reactions of Perfluoro Organic Compounds

Catalysts

Masato Ohashi¹ 

[1] Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan

关键词: C–F bond activation;    palladium;    perfluoroalkene;    perfluoroarene;    cross-coupling;    diarylzinc;    arylboronate;   

DOI  :  10.3390/catal4030321

来源: mdpi

【 摘 要 】

In this review, we summarize our recent development of palladium(0)-catalyzed cross-coupling reactions of perfluoro organic compounds with organometallic reagents. The oxidative addition of a C–F bond of tetrafluoroethylene (TFE) to palladium(0) was promoted by the addition of lithium iodide, affording a trifluorovinyl palladium(II) iodide. Based on this finding, the first palladium-catalyzed cross-coupling reaction of TFE with diarylzinc was developed in the presence of lithium iodide, affording α,β,β-trifluorostyrene derivatives in excellent yield. This coupling reaction was expanded to the novel Pd(0)/PR₃-catalyzed cross-coupling reaction of TFE with arylboronates. In this reaction, the trifluorovinyl palladium(II) fluoride was a key reaction intermediate that required neither an extraneous base to enhance the reactivity of organoboronates nor a Lewis acid additive to promote the oxidative addition of a C–F bond. In addition, our strategy utilizing the synergetic effect of Pd(0) and lithium iodide could be applied to the C–F bond cleavage of unreactive hexafluorobenzene (C₆F₆), leading to the first Pd(0)-catalyzed cross-coupling reaction of C₆F₆ with diarylzinc compounds.

【 授权许可】

CC BY   
© 2014 by the authors; licensee MDPI, Basel, Switzerland.