Hydroamination of C-C multiple bonds with hydrazine catalyzed by N-heterocyclic carbene-gold(I) complexes: Substrate and ligand effects

Almudena Couce-Rios, Gábor Kovács, Gregori Ujaque, Agustí Lledós

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30 Citations (Scopus)

Abstract

© 2014 American Chemical Society. In this work, we computationally address, from DFT calculations, mechanistic issues of the recently described hydroamination reactions catalyzed by (carbene) gold(I) complexes that use hydrazine as N-nucleophile. We have explored the hydrohydrazination of alkynes, alkenes, and allenes using three gold-carbene catalysts reported by Bertrand's and Hashmi's groups. Aspects such as the associative or dissociative nature of the ligand exchange between hydrazine and the substrate, the generation of the catalytically active π-complex, the inner- or outer-sphere mechanism for the nucleophilic attack, the nitrogen to carbon proton transfer or the relative importance of the ligand substitution, the nucleophile addition, and the proton transfer barriers in the catalytic cycle are analyzed in light of the DFT results, taking into account the nature of the carbene ligand and the substrate. The study can provide background for the design of further hydroamination reactions using simple small N-nucleophiles. (Chemical Presented).
Original languageEnglish
Pages (from-to)815-829
JournalACS Catalysis
Volume5
Issue number2
DOIs
Publication statusPublished - 6 Feb 2015

Keywords

  • DFT calculations
  • gold catalysis
  • hydrazine
  • hydroamination
  • N-heterocyclic carbene ligands

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