Lázaro-Milla, CarlosMascareñas Cid, José LuisLópez García, Fernando2024-04-242024-02-09ACS Catalalysis. 2024, 14, 5, 2872–2882http://hdl.handle.net/10347/33634This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © 2024 American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acscatal.3c05841.Readily available N-carbamoyl indolines can be converted into highly valuable 2-alkenyl and 2-alkyl indoles in a one-pot reaction, through an autotandem catalytic cascade promoted by an iridium complex. The process entails a dehydrogenation reaction initiated by an iridium-promoted C(sp3)–H activation, the addition of the resulting indole to an alkyne -or alkene-partner, and a spontaneous loss of the carbamoyl directing group. Interestingly, the resulting C2-alkenyl indoles can participate in a variety of metal-catalyzed annulations initiated by C–H activation, including formal [4 + 1] and [4 + 2] cycloadditions, as well as cross-dehydrogenative cyclizations, thus enabling a divergent access to a collection of functionally rich nitrogen-containing heterocycles.engAttribution-NonCommercial-NoDerivatives 4.0 Internacionalhttp://creativecommons.org/licenses/by-nc-nd/4.0/IridiumHydroarylationIndolesC-H functionalizationCycloadditionsjournal article10.1021/acscatal.3c058412155-5435open access