Hydrofluoroarylation of alkynes with fluoroarenes

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

Research output: Contribution to journalArticle

47 Citations (Scopus)

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
Externally publishedYes

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Alkynes
Fluorine
Alkenylation
Fluorobenzenes
Electrons
Nickel
Labeling
Chemical activation
Atoms
Catalysts
Experiments
ethylene

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Kanyiva, S. K., 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

Hydrofluoroarylation of alkynes with fluoroarenes. / Kanyiva, Stephen Kyalo; Kashihara, Natsuko; Nakao, Yoshiaki; Hiyama, Tamejiro; Ohashi, Masato; Ogoshi, Sensuke.

In: Dalton Transactions, Vol. 39, No. 43, 21.11.2010, p. 10483-10494.

Research output: Contribution to journalArticle

Kanyiva, SK, Kashihara, N, Nakao, Y, Hiyama, T, Ohashi, M & Ogoshi, S 2010, 'Hydrofluoroarylation of alkynes with fluoroarenes', Dalton Transactions, vol. 39, no. 43, pp. 10483-10494. https://doi.org/10.1039/c0dt00104j
Kanyiva SK, Kashihara N, Nakao Y, Hiyama T, Ohashi M, Ogoshi S. Hydrofluoroarylation of alkynes with fluoroarenes. Dalton Transactions. 2010 Nov 21;39(43):10483-10494. https://doi.org/10.1039/c0dt00104j
Kanyiva, Stephen Kyalo ; Kashihara, Natsuko ; Nakao, Yoshiaki ; Hiyama, Tamejiro ; Ohashi, Masato ; Ogoshi, Sensuke. / Hydrofluoroarylation of alkynes with fluoroarenes. In: Dalton Transactions. 2010 ; Vol. 39, No. 43. pp. 10483-10494.
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