Our first Angew. Chem. Int. Ed. for 2024, and second collaborative paper of the year, is already available on-line

06/03/2024

We are so happy to announce here that our collaborative research article at Angew. Chem. Int Ed., entitled "Gold(III) Auracycles featuring C(sp3)−Au−C(sp2) Bonds: Synthesis and Mechanistic Insights into the Cycloauration Step" and authored by J. A. González, A. Arribas, P. Tian, S. Díaz-Alonso, J. L. Mascareñas, F. López and C. Nevado, has been accepted and it's already on-line (gold Open Access).


Abstract: The direct auration of arenes is a key step in numerous gold-catalyzed reactions. Although reported more than 100 years ago, understanding of its underlying mechanism has been hampered by the difficulties in the isolation of relevant intermediates given the propensity of gold(III) species to undergo reductive elimination. Here, we report the synthesis and isolation of a new family of intriguing zwitterionic [C(sp3)^C(sp2)]-auracyclopentanes, as well as of their alkyl-gold(III) precursors and demonstrate their value as mechanistic probes to study the Csp2-Au bond-forming event. Experimental investigations employing Kinetic Isotope Effects (KIE), Hammett plot, and Eyring analysis provided important insights into the formation of the auracycle. The data suggest a SEAr mechanism wherein the slowest step might be the p-coordination between the arene and the gold(III) center, en route to the Wheland intermediate. We also show that these auracyclopentanes can work as catalysts in several gold-promoted transformations.






External link: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202402798