Arribas Domingo, AndrésCalvelo Souto, MartínFernández Fernández, DavidRodrigues, Catarina A. B.Mascareñas Cid, José LuisLópez García, Fernando2021-07-272021-07-272021Arribas, A., Calvelo, M., Fernández, D.F., Rodrigues, C.A.B., Mascareñas, J.L. and López, F. (2021), Highly Enantioselective Iridium(I)-Catalyzed Hydrocarbonation of Alkenes: A Versatile Approach to Heterocyclic Systems Bearing Quaternary Stereocenters. Angew. Chem. Int. Ed.. https://doi.org/10.1002/anie.2021057761433-7851http://hdl.handle.net/10347/26623We report a versatile, highly enantioselective intramolecular hydrocarbonation reaction that provides a direct access to heteropolycyclic systems bearing chiral quaternary carbon stereocenters. The method, which relies on an iridium(I)/bisphosphine chiral catalyst, is particularly efficient for the synthesis of five-, six- and seven-membered fused indole and pyrrole products, bearing one and two stereocenters, with enantiomeric excesses of up to >99 %. DFT computational studies allowed to obtain a detailed mechanistic profile and identify a cluster of weak non-covalent interactions as key factors to control the enantioselectivityeng© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are madeAttribution-NonCommercial-NoDerivatives 4.0 Internacionalhttp://creativecommons.org/licenses/by-nc-nd/4.0/C-H activationEnantioselectiveHeterocyclesHydrocarbonationIridiumjournal article10.1002/anie.2021057761521-3773open access