5 years ago

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

On the Accessible Reaction Channels of Vinyl Gold(I) Species: π- and σ-Pathways
Gerald Knizia, Johannes E. M. N. Klein, A. Stephen K. Hashmi, Laura Nunes dos Santos Comprido, Johannes Kästner
The potential of vinyl Au species to react either through a controlled π- or σ-pathway is demonstrated. This nomenclature is directly derived from the orbitals of the vinyl Au species leading to the newly formed bonds. When the π-bond of the vinyl Au intermediate is transformed into a σ-bond, we name it π-pathway, and a σ- to σ- transformation is named σ-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. One intermediate, two reaction channels: Following the intrinsic reaction coordinates of a Au-catalysed sigmatropic rearrangement and a protodeauration reaction, two different reaction pathways were found aided by intrinsic bond orbital analysis, showing the versatility of vinyl gold species in the context of catalysis.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201702023

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