Rhodium-NHC-Catalyzed gem-Specific O-Selective Hydropyridonation of Terminal Alkynes

Galiana-Cameo, Maria (Universidad de Zaragoza) ; Romeo, Raul ; Urriolabeitia, Asier (Universidad de Zaragoza) ; Passarelli, Vincenzo ; Perez-Torrente, Jesus J. (Universidad de Zaragoza) ; Polo, Victor (Universidad de Zaragoza) ; Castarlenas, Ricardo

Resumen: The 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.

Idioma: Inglés

DOI: 10.1002/anie.202117006

Año: 2022

Publicado en: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 61, 20 (2022), e2021170 [5 pp]
ISSN: 1433-7851

Factor impacto JCR: 16.6 (2022)

Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 13 / 178 = 0.073 (2022) - Q1 - T1

Factor impacto CITESCORE: 26.3 - Chemistry (Q1) - Chemical Engineering (Q1)

Factor impacto SCIMAGO: 5.573 - Chemistry (miscellaneous) (Q1) - Catalysis (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R
Financiación: info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PGC2018-099383-B-I00

Tipo y forma: Article (Published version)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)
Área (Departamento): Área Química Física (Dpto. Química Física)