Hiyama coupling reaction of fluorous alkenyl-fluorosilanes

Scope and mechanistic considerations

J. Rábai, Ágnes Csapó, A. Bodor

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Novel fluorous alkenyl-fluorosilanes (C nF 2n+1CHCHSiMe 2F; n = 4, 6, 8; 5a-c) were synthetized in a three step procedure from perfluoroalkyliodides and dimethylvinylchlorosilane. They were first reacted with iodobenzene at room temperature in Hiyama coupling reaction (DMF, Pd(OAc) 2, TBAF, 72 h) to afford the appropriate ω-perfluoroalkyl-styrenes (C nF 2n+1CHCHC 6H 5, n = 4, 6, 8); then the reactivity of 5a with monosubstituted iodobenzenes was studied. The coupling reaction of 5a with o-substituted iodobenzenes usually failed, while that of with the m- and p-substituted ones gave fluorous styrenes [m- or p-(C 4F 9CHCH)C 6H 4X], independently of the electronic effect of their substituent (X = Br, CF 3, CH 3, OCH 3). These volatile products can easily be isolated by steam-distilltaion and purified further by distillation. The mechanism of the above coupling reactions was a pure Hiyama type involving fluoride-ion induced transmetallation without any Heck type contribution, since no coupling product of C 6F 13CHCH 2 and C 6H 5I was observed in blank control experiments using similar conditions (DMF, TBAF, Pd(OAc) 2, 72 h, 25°C).

Original languageEnglish
Pages (from-to)85-92
Number of pages8
JournalJournal of Fluorine Chemistry
Volume137
DOIs
Publication statusPublished - May 2012

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Iodobenzenes
Styrenes
Distillation
Steam
distillation
Fluorides
styrenes
fluoride
Ions
Temperature
ion
blanks
products
steam
fluorides
reactivity
experiment
temperature
Experiments
methylidyne

Keywords

  • Fluorous styrenes
  • Hiyama coupling
  • Perfluoroalkylation at room temperature
  • Steam-distillation

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Environmental Chemistry

Cite this

Hiyama coupling reaction of fluorous alkenyl-fluorosilanes : Scope and mechanistic considerations. / Rábai, J.; Csapó, Ágnes; Bodor, A.

In: Journal of Fluorine Chemistry, Vol. 137, 05.2012, p. 85-92.

Research output: Contribution to journalArticle

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