Mechanistic investigations of palladium-catalyzed allylic fluorination

Matthew H. Katcher, Per Ola Norrby, Abigail Gutmann Doyle

Research output: Contribution to journalArticle

39 Citations (Scopus)

Abstract

A computational and experimental approach was employed to study the mechanism of the palladium(0)-catalyzed fluorination of allylic chlorides with AgF as fluoride source. Our findings indicate that an allylpalladium fluoride is a key intermediate necessary for the generation of both the nucleophile and electrophile. Evidence was also obtained to support a homobimetallic mechanism in which C-F bond formation occurs by nucleophilic attack of a neutral allylpalladium fluoride on a cationic allylpalladium electrophile (with fluoride as counterion). The high branched selectivity and unusual ligand effects observed in the regioselective fluorination are assessed in light of this mechanism and calculated transition states. These results may have important implications for the mechanism of other transition-metal-catalyzed fluorinations.

Original languageEnglish (US)
Pages (from-to)2121-2133
Number of pages13
JournalOrganometallics
Volume33
Issue number9
DOIs
StatePublished - May 12 2014

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Fluorination
fluorination
Palladium
Fluorides
fluorides
palladium
Nucleophiles
nucleophiles
attack
Transition metals
Chlorides
selectivity
transition metals
chlorides
Ligands
ligands

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Katcher, Matthew H. ; Norrby, Per Ola ; Doyle, Abigail Gutmann. / Mechanistic investigations of palladium-catalyzed allylic fluorination. In: Organometallics. 2014 ; Vol. 33, No. 9. pp. 2121-2133.
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Mechanistic investigations of palladium-catalyzed allylic fluorination. / Katcher, Matthew H.; Norrby, Per Ola; Doyle, Abigail Gutmann.

In: Organometallics, Vol. 33, No. 9, 12.05.2014, p. 2121-2133.

Research output: Contribution to journalArticle

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