2026-04-14T05:47:35Zhttps://recercat.cat/oai/request

oai:recercat.cat:2072/4890642026-02-17T09:55:00Zcom_2072_300912com_2072_4427col_2072_301309

Dual Co/Photoredox-Catalyzed Regio- and Stereoselective Synthesis of Highly Functional 1,3-Dienes Tóth, Balázs L. Delgado, Alejandro Ghorai, Debasish Meneses, Diego García-Camacho, Aimara Vicent-Morales, Maria Benet-Buchholz, Jordi Funes-Ardoiz, Ignacio Kleij, Arjan W. Química 54 A dual Co/photoredox catalytic coupling of 1,3-enynes and α,ß-unsaturated aliphatic aldehydes and ketones has been developed that creates access to highly functional 1,3-diene synthons through a regio- and stereoselective carbon-carbon coupling process. The scope of the process features diverse functionalized scaffolds with a high degree of molecular complexity. The synthetic utility of these 1,3-dienes is demonstrated including a telescoped, one-pot approach using an alkynyl cyclic carbonate as a 1,3-enyne surrogate offering direct access to the 1,3-diene product. Mechanistic analysis involving control reactions, deuterium labeling studies and DFT calculations are in line with the in situ formation of a Co─H species and an outer-sphere coupling pathway in which a regio- and stereoselective coupling occurs between a dienyl radical and carbonyl species. info:eu-repo/semantics/acceptedVersion 2025-12-21 info:eu-repo/semantics/article http://hdl.handle.net/2072/489064 https://doi.org/10.1002/anie.202522561 eng CERCA Program/Generalitat de Catalunya ICREA Foundation MICIU/AEI (PID2023-149295NB-I00, RED2022-134074-T and Severo Ochoa Excellence Accreditation CEX2024-001469-S) AGAUR (2021-SGR-00853) B.L.T. acknowledges support from the European Union's Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement 101026029 A.D. thanks MICINN for a predoctoral fellowship (PRE2021-100384) A.G.-C and I.F.A thank MICIU/AEI/ 10.13039/501100011033 and Feder/EU for funding of the projects PID2021-126075NB-I00 and MICIU/AEI/10.13039/501100011033, and FSE + for a Ramón y Cajal fellowship (RYC2022–035776-I) A.G-C. thanks the University of La Rioja and La Rioja Government for a predoctoral fellowship within the 2025 call. Attribution 4.0 International http://creativecommons.org/licenses/by/4.0/ info:eu-repo/semantics/embargoedAccess 13 p. application/pdf Wiley RECERCAT (Dipòsit de la Recerca de Catalunya)