Computational Characterization of the Mechanism for the Oxidative Coupling of Benzoic Acid and Alkynes by Rhodium/Copper and Rhodium/Silver Systems

Ignacio Funes-Ardoiz, Feliu Maseras

Research output: Contribution to journalArticleResearchpeer-review

12 Citations (Scopus)

Abstract

© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim DFT calculations were applied to study the oxidative coupling between benzoic acid and 1-phenyl-1-propyne catalyzed by [CpRhCl2]2 (Cp=cyclopentadienyl) by using either Cu(OAc)2(H2O) or Ag(OAc) as the terminal oxidant, a process that has been experimentally shown to have subtleties related to regioselectivity (placement of the phenyl substituent of the alkyne in the isocoumarin product) and chemoselectivity (isocoumarin or naphthalene derivatives). Calculations reproduced the experimental results and showed the involvement of the oxidant throughout the catalytic cycle. The regioselectivity was found to be decided in the alkyne insertion step, in particular by the relative arrangement of the two phenyl groups. The high chemoselectivity towards isocoumarin associated to Cu(OAc)2(H2O) could be explained by the fact that the copper moiety blocks the CO2 extrusion pathway, which would lead to naphthalene derivatives, something that does not happen if Ag(OAc) is used.
Original languageEnglish
Pages (from-to)12383-12388
JournalChemistry - A European Journal
Volume24
Issue number47
DOIs
Publication statusPublished - 22 Aug 2018

Keywords

  • chemoselectivity
  • density functional calculations
  • oxidant effect
  • oxidative coupling
  • reaction mechanisms

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