Hydrofluoroarylation of alkynes with fluoroarenes

Kyalo Stephen Kanyiva, Natsuko Kashihara, Yoshiaki Nakao, Tamejiro Hiyama, Masato Ohashi, Sensuke Ogoshi

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Abstract

A combination of Ni(cod)2 and PCyp3 is found to be an effective catalyst for chemoselective activation of the C-H bond of fluoroarenes over C-F bonds followed by insertion of alkynes to allow direct alkenylation of the electron-deficient arenes. The characteristics of the reactions are: a C-H bond ortho to a fluorine substituent is selectively activated; the reactivity of fluorobenzenes is roughly proportional to the number of fluorine atoms. The reaction conditions tolerate a broad range of both alkynes and fluoroarenes containing both electron-withdrawing and -donating groups, thus allowing efficient synthesis of a variety of substituted ethenes containing a fluoroaryl motif in high regio- and stereoselective manners. Mechanistic studies including both labeling experiments and stoichiometric reactions reveal that oxidative addition of C-H bonds in fluoroarenes to nickel(0) is kinetically highly facile whereas that of C-F bonds is thermodynamically favoured.

Original languageEnglish
Pages (from-to)10483-10494
Number of pages12
JournalDalton Transactions
Volume39
Issue number43
DOIs
Publication statusPublished - 2010 Nov 21

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ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Kanyiva, K. S., Kashihara, N., Nakao, Y., Hiyama, T., Ohashi, M., & Ogoshi, S. (2010). Hydrofluoroarylation of alkynes with fluoroarenes. Dalton Transactions, 39(43), 10483-10494. https://doi.org/10.1039/c0dt00104j