Ruthenium–arene catalysts bearing N-heterocyclic carbene ligands for olefin cyclopropanation and metathesis

Abstract

Ruthenium–arene complexes bearing N-heterocyclic carbene (NHC) ligands with the generic formula [RuCl2(p-cymene)(NHC)] are efficient catalyst precursors for the cyclopropanation of activated olefins with ethyl diazoacetate, and the cis/trans diastereoselectivity of the reaction markedly depends on the steric bulk of the NHC. The procedure was successfully applied to styrene, α-methylstyrene, and various other styrenic derivatives bearing electron-withdrawing or donating substituents on their aromatic rings. The reaction of unactivated internal or terminal alkenes was more sluggish, and the use of norbornene as a substrate afforded only olefin metathesis. Further investigation of the ring-opening metathesis polymerization of this strained cycloolefin in the presence of trimethylsilyldiazomethane led to high molecular weight polynorbornene whose microstructure was not significantly affected by the choice of the NHC ancillary ligand.

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Acknowledgments

The financial support of the “Fonds de la Recherche Scientifique-FNRS,” Brussels, is gratefully acknowledged.

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Correspondence to Lionel Delaude.

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Dedicated to the lifework of Professor Franz Stelzer and his achievements in olefin metathesis and polymer chemistry.

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Méret, M., Maj, A.M., Demonceau, A. et al. Ruthenium–arene catalysts bearing N-heterocyclic carbene ligands for olefin cyclopropanation and metathesis. Monatsh Chem 146, 1099–1105 (2015). https://doi.org/10.1007/s00706-015-1492-x

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Keywords

  • Arene complexes
  • Cross-metathesis
  • para-Cymene
  • Homogeneous catalysis
  • Ring-opening metathesis polymerization
  • Structure–activity relationships