Second contribution of our group to JACS in this beginning of 2026
05/07/2026We are so pleased to announce here that our most recent research article at J. Am. Chem. Soc., entitled "Enantioselective Iridium-Catalyzed Intramolecular Hydroarylation of (Hetero)Arene-Tethered Prochiral Diketones" and authored by A. Arribas, C. Lázaro-Milla, M. Calvelo, J. L. Mascareñas and F. López, has been accepted and it's already on-line (gold Open Access).
Abstract: The enantioselective iridium(I)-catalyzed hydroarylation of C–C unsaturated bonds ranks among the most atom-efficient technologies in organic synthesis. We now report an enantioselective desymmetrizing cyclization that entails carbonyls instead of C═C partners, providing direct access to architecturally complex (hetero)polycyclic frameworks bearing a tertiary alcohol and an adjacent all-carbon quaternary stereocenter at their ring junctions. The in situ dehydration of the initially formed alcohol was occasionally observed to yield products bearing an allylic quaternary stereocenter, which offers excellent opportunities for downstream functionalization. Mechanistically intriguing, we demonstrated that this dehydration can be suppressed by adding Et3SiH, an additive that also accelerates the overall transformation. Computational studies support a carbometalation/O–H reductive elimination pathway and shed light on the stereochemical origin of the enantioselectivity.
External link: https://pubs.acs.org/doi/10.1021/jacs.6c05640