Synthesis of benzylpalladium complexes through C-O bond cleavage of benzylic carboxylates

Development of a novel palladium-catalyzed benzylation of olefins

Hirohisa Narahashi, Isao Shimizu, Akio Yamamoto

Research output: Contribution to journalArticle

51 Citations (Scopus)

Abstract

Benzylic carboxylates were found to react with Pd(0) complexes bearing tertiary phosphines to give benzylpalladium(II) carboxylate complexes with cleavage of the benzyl-oxygen bond. The benzylpalladium complexes having the trifluoroacetato ligand react with olefins such as ethyl acrylate to give olefin benzylation products. On the basis of these studies a novel palladium-catalyzed benzylation of olefins was developed without using organic halides as the starting materials. The method has another advantage of requiring no base as in the conventional Mizoroki-Heck process using organic halides. The catalytic cycle is proposed to be constituted of elementary processes of (a) oxidative addition of a benzyl carboxylate with C-O bond cleavage to a Pd(0) complex to give a benzylpalladium carboxylate, (b) olefin insertion into the benzylpalladium bond to give an alkylpalladium complex, and (c) β-H abstraction to liberate the benzylated olefin.

Original languageEnglish
Pages (from-to)283-296
Number of pages14
JournalJournal of Organometallic Chemistry
Volume693
Issue number2
DOIs
Publication statusPublished - 2008 Jan 15

Fingerprint

Palladium
Alkenes
carboxylates
alkenes
Olefins
palladium
cleavage
synthesis
halides
Bearings (structural)
Phosphines
acrylates
phosphines
insertion
Ligands
Oxygen
ligands
cycles
oxygen
products

Keywords

  • Benzyl-O bond cleavage, Olefin synthesis
  • Benzylation
  • Benzylpalladium carboxylate
  • Palladium catalyst

ASJC Scopus subject areas

  • Chemical Engineering (miscellaneous)
  • Materials Science (miscellaneous)
  • Materials Chemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Biochemistry

Cite this

Synthesis of benzylpalladium complexes through C-O bond cleavage of benzylic carboxylates : Development of a novel palladium-catalyzed benzylation of olefins. / Narahashi, Hirohisa; Shimizu, Isao; Yamamoto, Akio.

In: Journal of Organometallic Chemistry, Vol. 693, No. 2, 15.01.2008, p. 283-296.

Research output: Contribution to journalArticle

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