On the Accessible Reaction Channels of Vinyl Gold(I) Species: Pi- and sigma-Pathways

Laura Nunes dos Santos Comprido, Johannes E. M. N. Klein, Gerald Knizia, Johannes Kaestner, A. Stephen K. Hashmi*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

28 Citations (Scopus)

Abstract

The potential of vinyl Au species to react either through a controlled pi- or sigma-pathway is demonstrated. This nomenclature is directly derived from the orbitals of the vinyl Au species leading to the newly formed bonds. When the pi-bond of the vinyl Au intermediate is transformed into a sigma-bond, we name it pi-pathway, and a sigma- to sigma- transformation is named s- pathway. Examples of reactions following these pathways are a Au-catalysed [3,3]-sigmatropic rearrangement and a protodeauration reaction. These reactions have been studied using intrinsic bond orbitals (IBOs) and allow for the clear identification of these pathways. Energies for the reaction path of the Au-catalysed [3,3]-sigmatropic rearrangement were in addition computed using CCSD(T)-F12. Analysis of the intrinsic reaction coordinate (IRC) of the [3,3]-sigmatropic rearrangement using IBOs further allows us to refine the previous mechanistic proposal and identifies a hidden intermediate along the reaction path.

Original languageEnglish
Pages (from-to)10901-10905
Number of pages5
JournalChemistry
Volume23
Issue number45
DOIs
Publication statusPublished - 10-Aug-2017
Externally publishedYes

Keywords

  • alkenes
  • allyldeauration
  • computational chemistry
  • gold catalysis
  • protodeauration
  • CATALYZED CYCLOISOMERIZATION REACTIONS
  • DENSITY-FUNCTIONAL THEORY
  • CARBENE COMPLEXES
  • BASIS-SETS
  • STRUCTURAL-CHARACTERIZATION
  • ORGANOGOLD COMPLEXES
  • ORGANIC-REACTIONS
  • CYCLIZATION
  • ALKYNES
  • BOND

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