Palladium-catalyzed cross-coupling reactions with fluorinated substrates: Mechanistic insights into the undesired hydrodehalogenation of aryl halides

Meital Orbach, Joyanta Choudhury, Michal Lahav, Olena V. Zenkina, Yael Diskin-Posner, Gregory Leitus, Mark A. Iron, Milko van der Boom

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

We report here that the undesired hydrodehalogenation in cross-coupling reactions with fluorinated substrates involves water as a possible hydrogen source. Moreover, the product distribution (hydrodehalogenation vs carbon-carbon coupling) can be controlled by varying the phosphine substituents. Significant hydrodehalogenation occurs prior to the formation of Ar F-Pd(II)-Br complexes. DFT calculations were used to evaluate a direct hydrodehalogenation route with a phosphine and water. These findings provide new mechanistic insight into aryl-Br bond activation with fluorinated substrates and selective arene functionalization.

Original languageEnglish
Pages (from-to)1271-1274
Number of pages4
JournalOrganometallics
Volume31
Issue number4
DOIs
Publication statusPublished - Feb 27 2012

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phosphine
cross coupling
Palladium
phosphines
halides
palladium
Carbon
Water
carbon
Substrates
Discrete Fourier transforms
water
Hydrogen
Chemical activation
routes
activation
hydrogen
products

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Palladium-catalyzed cross-coupling reactions with fluorinated substrates : Mechanistic insights into the undesired hydrodehalogenation of aryl halides. / Orbach, Meital; Choudhury, Joyanta; Lahav, Michal; Zenkina, Olena V.; Diskin-Posner, Yael; Leitus, Gregory; Iron, Mark A.; van der Boom, Milko.

In: Organometallics, Vol. 31, No. 4, 27.02.2012, p. 1271-1274.

Research output: Contribution to journalArticle

Orbach, Meital ; Choudhury, Joyanta ; Lahav, Michal ; Zenkina, Olena V. ; Diskin-Posner, Yael ; Leitus, Gregory ; Iron, Mark A. ; van der Boom, Milko. / Palladium-catalyzed cross-coupling reactions with fluorinated substrates : Mechanistic insights into the undesired hydrodehalogenation of aryl halides. In: Organometallics. 2012 ; Vol. 31, No. 4. pp. 1271-1274.
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