A Metal-Ligand Cooperative Pathway for Intermolecular Oxa-Michael Additions to Unsaturated Nitriles

Sebastien Perdriau, Douwe S. Zijlstra, Hero J. Heeres, Johannes G. de Vries*, Edwin Otten

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

47 Citations (Scopus)
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Abstract

An unprecedented catalytic pathway for oxa-Michael addition reactions of alcohols to unsaturated nitriles has been revealed using a PNN pincer ruthenium catalyst with a dearomatized pyridine backbone. The isolation of a catalytically competent Ru-dieneamido complex from the reaction between the Ru catalyst and pentenenitrile in combination with DFT calculations supports a mechanism in which activation of the nitrile through metal-ligand cooperativity is a key step. The nitrile-derived Ru-N moiety is sufficiently Bronsted basic to activate the alcohol and initiate conjugate addition of the alkoxide to the alpha, beta-unsaturated fragment. This reaction proceeds in a concerted manner and involves a six-membered transition state. These features allow the reaction to proceed at ambient temperature in the absence of external base.

Original languageEnglish
Pages (from-to)4236-4240
Number of pages5
JournalAngewandte Chemie - International Edition
Volume54
Issue number14
DOIs
Publication statusPublished - 27-Mar-2015

Keywords

  • homogeneous catalysis
  • Michael addition
  • non-innocent ligands
  • pincer ligands
  • ruthenium
  • PINCER COMPLEXES
  • BOND FORMATION
  • N-H
  • CONJUGATE ADDITIONS
  • ACTIVATED ALKENES
  • ALCOHOLS
  • CATALYSIS
  • OLEFINS
  • AMINES
  • RU

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