Fernández Fernández, DavidRodrigues, Catarina A. B.Calvelo Souto, MartínGulías Costa, MoisésMascareñas Cid, José LuisLópez García, Fernando2018-10-082019-01-102018-07-10Fernández, D., Rodrigues, C., Calvelo, M., Gulías, M., Mascareñas, J., & López, F. (2018). Iridium(I)-Catalyzed Intramolecular Cycloisomerization of Enynes: Scope and Mechanistic Course. ACS Catalysis, 8(8), 7397-7402. doi: 10.1021/acscatal.8b02139http://hdl.handle.net/10347/17408NOTICE: This is the peer reviewed version of the following article: David F. Fernández, Catarina A. B. Rodrigues, Martín Calvelo, Moisés Gulías, José L. Mascareñas and Fernando López (2018), Iridium(I)-Catalyzed Intramolecular Cycloisomerization of Enynes: Scope and Mechanistic Course. ACS Catalysis, 2018, 8 (8), 7397–7402 [DOI: 10.1021/acscatal.8b02139]. This article may be used for non-commercial purposes in accordance with American Chemical Society Terms and Conditions for self-archivingWe report an Ir(I)-catalyzed cycloisomerization methodology that provides access to carbocyclic systems bearing exo-alkene moieties from alkynyl-equipped acyclic precursors. The method relies on the C–H activation of olefinic and (hetero)aromatic C(sp2)–H bonds, followed by an exocyclization to a tethered alkyne, and provides interesting cyclic diene products that are amenable of further elaboration. Importantly, DFT calculations suggests that, in contrast to related hydrocarbonations of alkenes in which either migratory insertions or C–C reductive eliminations have been suggested to be rate-determining, in our reactions, the energetic barrier of these steps is lower than that of the previous C–H activationeng© 2018 American Chemical SocietyCatalysisCyclizationC−H activationHydrocarbonationIridiumjournal article10.1021/acscatal.8b021392155-5435open access