Influence of a Very Bulky <i>N-</i>Heterocyclic Carbene in Gold-Mediated Catalysis

Abstract

The syntheses of the free carbene IPr* (IPr* = 1,3-bis(2,6-bis(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene) and related gold complexes [Au(IPr*)Cl] ( C1 ) and [Au(IPr*)(NTf 2 )] ( C2 ) were achieved in high yields. The % V Bur of IPr* for both gold complexes was measured, revealing IPr* as one of the bulkiest NHCs on gold complexes reported to date. In addition, the catalytic activity of C1 and C2 in several reactions, typically catalyzed by Au I complexes, was investigated. Examples include the tandem alkoxylation/lactonization of γ-hydroxy-α,β-acetylenic esters, the [3,3]-rearrangement of propargylic acetates leading to the formation of conjugated enones and substituted indenes, and the rearrangement of allylic acetates. These studies revealed a strong solvent effect on the catalytic activity with 1,2-dichloroethane as the solvent of choice. The screening of C1 and C2 demonstrated only slightly diminished activities in comparison to [Au(NHC)(L)] complexes bearing bulky ligands such as IPr and SIPr.