doi:10.1002/anie.202117006engGaliana-Cameo, MariaRomeo, RaulUrriolabeitia, AsierPassarelli, VincenzoPerez-Torrente, Jesus J.Polo, VictorCastarlenas, RicardoRhodium-NHC-Catalyzed gem-Specific O-Selective Hydropyridonation of Terminal AlkynesART-2022-128688The dinuclear complex Rh(mu-Cl)(eta(2)-coe)(IPr)](2) is an efficient catalyst for the O-selective Markovnikov-type addition of 2-pyridones to terminal alkynes. DFT calculations support a hydride-free pathway entailing intramolecular oxidative protonation of a pi-alkyne by a kappa N-1-hydroxypyridine ligand. Subsequent O-nucleophilic attack on a metallacyclopropene species affords an O-alkenyl-2-oxypyridine chelate rhodium intermediate as the catalyst resting state. The release of the alkenyl ether is calculated as the rate-determining step.2022http://zaguan.unizar.es/record/11743710.1002/anie.202117006http://zaguan.unizar.es/record/117437oai:zaguan.unizar.es:117437info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20Rinfo:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00info:eu-repo/grantAgreement/ES/MICINN/PGC2018-099383-B-I00ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 61, 20 (2022), e2021170 [5 pp]by-nc-ndhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/info:eu-repo/semantics/openAccess