Au(III) catalyzes the cross-coupling between activated methylenes and alkene derivatives

• Published in: Journal of catalysis 2020-12, Vol.392, p.159-164
• Main Authors: Castiñeira Reis, Marta, Marín-Luna, Marta, Janković, Nenad, Nieto Faza, Olalla, Silva López, Carlos
• Format: Article
• Language: English
• Subjects: C[sbnd]C bond formation; Cross-coupling; Gold catalysis
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2020.09.030

[Display omitted] •Au(III) can catalyze CC cross-coupling processes via CH activation steps.•Au(III) is more efficient than Au(I) when b-elimination steps are involved.•Evidence-based reaction mechanisms backed by computational simulation.•Au(III) catalyzes cross coupling in a single oxidation state mechanism. In the last decade substantial efforts were devoted towards the exploitation of the Au(I) as a promising tool to promote CC bond formation reactions via the activation of unsaturations. Among these efforts, Au(I)/Au(III) cross couplings mediated by a co-oxidant or by photoactivation sit at a privileged position. Au(III) has also shown a rich chemistry but, due to its hardness and lower affinity for unsaturations, it is less often the catalyst of choice in CC bond forming strategies. Surprisingly, we have recently found two examples of cross-coupling reactions in which the authors report to be adding Au(III) to the reaction flask while claiming that Au(I) is the species responsible for the catalytic events. One of such cases even occurs under oxidizing conditions. Here we present a detailed computational study in which we explore the mechanism behind these CC forming reactions. Our results suggest that Au(III) can efficiently catalyze these transformations, thus invoking this exotic reduction is not only unnecessary but also energetically unfavourable.