Dynamic Configuration on a Chiral-at-Rhodium Catalyst Featuring a Flexible Tetradentate Ligand

Tejero, Álvaro G. ; Castillo, Javier ; Viguri, Fernando (Universidad de Zaragoza) ; Carmona, Daniel ; Passarelli, Vincenzo ; Lahoz, Fernando J. ; García-Orduña, Pilar ; Rodríguez, Ricardo

Resumen: The unique dynamic configuration of an enantioselective chiral‐at‐metal catalyst based on Rh(III) and a non‐chiral tetradentate ligand is described and resolved. At room temperature, the catalyst undergoes a dynamic configuration process leading to the formation of two interconvertible metal‐stereoisomers, remarkably without racemization. Density functional theory (DFT) calculations indicate that this metal‐isomerization proceeds via a concerted transition state, which features a trigonal bipyramidal geometry stabilized by the tetradentate ligand. Furthermore, the resolved enantiopure complex shows high catalytic enantioinduction in the Friedel‐Crafts reaction, achieving enantiomeric ratios as high as 99 : 1.

Idioma: Inglés

DOI: 10.1002/chem.202303935

Año: 2024

Publicado en: Chemistry - A European Journal 30, 10 (2024), 202303935 [6 pp.]
ISSN: 0947-6539

Factor impacto SCIMAGO: 1.058 - Chemistry (miscellaneous) (Q1) - Organic Chemistry (Q1) - Catalysis (Q2)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E05-23R
Financiación: info:eu-repo/grantAgreement/ES/MCIU-AEI-FEDER/PID2021-122406NB-100
Financiación: info:eu-repo/grantAgreement/ES/MCIU/RED2018-102574-T
Financiación: info:eu-repo/grantAgreement/ES/MICINN/CTQ2018-095561-BI00

Tipo y forma: Article (PostPrint)

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