Catalytic system for the Heck reaction of fluorinated haloaryls

Ana C. Albéniz, Pablo Espinet, Blanca Martín-Ruiz, David Milstein

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

A catalytic system for the Heck reaction of fluorinated haloaryls, which involves the first catalytic insertion into a metal-perfluoroaryl bond, has been developed. Pentafluorophenyl complexes of palladium which lack ligands other than halides are used as catalysts. The absence of other ligands besides solvent, halides, and substrates is required for an efficient functionalization. Pentafluoro- and tetrafluoro-substituted haloaryls can be efficiently reacted with terminal and disubstituted olefins, such as styrene, α-methylstyrene, and acrylate esters, but nonactivated alkenes give only moderate yields. Coordination-insertion is rate determining for pentafluoroaryl and tetrafluoroaryl bromides, which can be switched to oxidative addition if a large excess of olefin is used. Thus, the best reaction conditions can be reached by adjusting the actual ratio of haloaryl to olefin for each combination of substrates.

Original languageEnglish
Pages (from-to)3679-3684
Number of pages6
JournalOrganometallics
Volume24
Issue number15
DOIs
Publication statusPublished - Jul 18 2005

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Alkenes
alkenes
halides
insertion
Ligands
ligands
Styrene
Palladium
Substrates
acrylates
Bromides
styrenes
palladium
bromides
esters
Esters
Metals
adjusting
catalysts
Catalysts

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Catalytic system for the Heck reaction of fluorinated haloaryls. / Albéniz, Ana C.; Espinet, Pablo; Martín-Ruiz, Blanca; Milstein, David.

In: Organometallics, Vol. 24, No. 15, 18.07.2005, p. 3679-3684.

Research output: Contribution to journalArticle

Albéniz, AC, Espinet, P, Martín-Ruiz, B & Milstein, D 2005, 'Catalytic system for the Heck reaction of fluorinated haloaryls', Organometallics, vol. 24, no. 15, pp. 3679-3684. https://doi.org/10.1021/om050017w
Albéniz, Ana C. ; Espinet, Pablo ; Martín-Ruiz, Blanca ; Milstein, David. / Catalytic system for the Heck reaction of fluorinated haloaryls. In: Organometallics. 2005 ; Vol. 24, No. 15. pp. 3679-3684.
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