Chemodivergent Metathesis of Dienynes Catalyzed by Ruthenium-Indenylidene Complexes: An Experimental and Computational Study

Herve Clavier, Andrea Correa, Eduardo C. Escudero-Adan, Jordi Benet-Buchholz, Luigi Cavallo, Steven P. Nolan

Research output: Contribution to journalReview articlepeer-review

58 Citations (Scopus)

Abstract

A study on the enyne metathesis reaction leading to the formation cyclic compounds using ruthenium-indenylidene complexes is presented. Several 1,11-dien-6-ynes have been subjected to ruthenium metathesis cyclization by using ruthenium-indenylidene complexes hearing various phosphine 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 "enc-then-yne" of "yne-then-ene" reaction pathways apparently at play in these systems using both experimental observations and DFT calculations. Experimental and computational 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. fur catalysts bearing NHC ligands, both pathways are possible.

Original languageEnglish
Pages (from-to)10244-10254
Number of pages11
JournalChemistry - A European Journal
Volume15
Issue number39
DOIs
Publication statusPublished - 2009

Keywords

  • density functional calculations
  • enynes
  • homogeneous catalysis
  • metathesis
  • N-heterocycle carbenes
  • ruthenium
  • RING-CLOSING METATHESIS
  • N-HETEROCYCLIC CARBENE
  • OLEFIN METATHESIS
  • ENYNE METATHESIS
  • REARRANGEMENT METATHESIS
  • OPENING/CROSS-METATHESIS
  • LAURENCIA-MAJUSCULA
  • GRUBBS RUTHENIUM
  • CROSS-METATHESIS
  • NATURAL-PRODUCTS

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