Chemodivergent metathesis of dienynes catalyzed by ruthenium-indenylidene complexes: An experimental and computational study

Hervé Clavier, Andrea Correa, Eduardo C. Escudero-Adán, Benet Buchholz Jordi, Luigi Cavallo*, Steven P. Nolan

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

54 Scopus citations

Abstract

A study on the enyne meta-thesis reaction leading to the formation cyclic compounds using ruthenium-in-denylidene complexes is presented. Several l, 11-dien-6-ynes have been subjected to ruthenium metathesis cyc-lization by using ruthenium-indenyli-dene complexes bearing various phos-phine and N-heterocyclic carbene (NHC) ligands. Interestingly, for some substrates chemodivergent metathesis occurs and is a function of the catalyst employed. This led us to investigate the competing "ene-then-yne" or "yne-then-ene" reaction pathways apparent-ly at play in these systems using both experimental observations and DFT calculations. Experimental and compu-tational studies were found in good agreement and permit to conclude that for phosphine-containing catalysts, the "ene-then-yne" pathway is exclusively adopted. On the other hand, for cata-lysts bearing NHC ligands, both path-ways are possible.

Original languageEnglish (US)
Pages (from-to)10244-10254
Number of pages11
JournalChemistry - A European Journal
Volume15
Issue number39
DOIs
StatePublished - Oct 5 2009

Keywords

  • Density functional calcu-lations
  • Enynes
  • Homogeneous catalysis
  • Metathesis
  • N-heterocyclic carbenes
  • Ruthenium

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

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