Room-Temperature Benzylic Alkylation of Benzylic Carbonates: Improvement of Palladium Catalyst and Mechanistic Study

Ryoichi Kuwano, Masashi Yokogi, Ken Sakai, Shigeyuki Masaoka, Takashi Miura, Sungyong Won

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)

Abstract

The palladium catalyst for the nucleophilic substitution of benzyl carbonates was improved by using 1,1′-bis(diisopropylphosphino)ferrocene (DiPrPF) as the ligand. The [Pd(η3-C3H5)(cod)]BF4-DiPrPF catalyst allows the benzylic substitution with soft carbanions to proceed even at 30 °C, affording the desired products in high yields (up to 99% yield). Thermally unstable pyridylmethyl esters are employable as the electrophilic substrates for the benzylic alkylation with the improved catalyst. Furthermore, we investigated the mechanism of the catalytic benzylic alkylation by means of DiPrPF ligand. The palladium(0) complex bearing DiPrPF activates the benzylic C-O bond to form the (benzyl)palladium(II) intermediate at room temperature. The coordination mode of the benzyl ligand would be equilibrium between the η1- and η3-manner. The nucleophile would preferentially react with the η3-benzyl ligand to give the desired product.

Original languageEnglish
Pages (from-to)1568-1579
Number of pages12
JournalOrganic Process Research and Development
Volume23
Issue number8
DOIs
Publication statusPublished - Aug 16 2019

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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