Concepción Vicente, Eduardo daFernández, IsraelMascareñas Cid, José LuisLópez García, Fernando2021-05-182022-01-192021E. Da Concepción, I. Fernández, J. L. Mascareñas, F. López, Angew. Chem. Int. Ed. 2021, 60, 8182.1433-7851http://hdl.handle.net/10347/26201This is the peer reviewed version of the following article: E. Da Concepción, I. Fernández, J. L. Mascareñas, F. López, Angew. Chem. Int. Ed. 2021, 60, 8182, which has been published in final form at https://doi.org/10.1002/anie.202015202. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived VersionsLow‐valent cobalt complexes equipped with chiral ligands can efficiently promote highly enantioselective (3+2) cycloadditions of alkyne‐tethered alkylidenecyclopropanes. The annulation allows to assemble bicyclic systems containing five‐membered rings in good yields and with excellent enantiomeric ratios. We also present a mechanistic discussion based on experimental and computational data, which support the involvement of CoI/CoIII catalytic cycleseng© 2021 Wiley‐VCH GmbH. This article may be used for non-commercial purposes in accordance with Wiley-VCH Terms and Conditions for Self-ArchivingAlkylidenecyclopropaneCobaltCycloadditionEarth-abundant metalsEnantioselectivityjournal article10.1002/anie.2020152021521-3773open access