Cooperative Reductive Elimination: The Missing Piece in the Oxidative-Coupling Mechanistic Puzzle

Ignacio Funes-Ardoiz, Feliu Maseras

Research output: Contribution to journalArticleResearchpeer-review

28 Citations (Scopus)

Abstract

© 2016 Wiley-VCH Verlag GmbH & Co. KGaA. The reaction between benzoic acid and methylphenylacetylene to form an isocoumarin is catalyzed by Cp∗Rh(OAc)2 in the presence of Cu(OAc)2(H2O) as an oxidant and a leading example of oxidative-coupling reactions. Its mechanism was elucidated by DFT calculations with the B97D functional. The conventional mechanism, with separate reductive-elimination and reoxidation steps, was found to yield a naphthalene derivative as the major product by CO2 extrusion, contradicting experimental observations. The experimental result was reproduced by an alternative mechanism with a lower barrier: In this case, the copper acetate oxidant plays a key role in the reductive-elimination step, which takes place through a transition state containing both rhodium and copper centers. This cooperative reductive-elimination step would not be accessible with a generic oxidant, which, again, is in agreement with available experimental data.
Original languageEnglish
Pages (from-to)2764-2767
JournalAngewandte Chemie - International Edition
Volume55
Issue number8
DOIs
Publication statusPublished - 18 Feb 2016

Keywords

  • C-C coupling
  • density functional calculations
  • oxidative coupling
  • reaction mechanisms
  • reductive elimination

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