Synthesis of chiral-at-metal rhodium complexes from achiral tripodal tetradentate ligands: resolution and application to enantioselective Diels–Alder and 1,3-dipolar cycloadditions

Tejero, Alvaro G. (Universidad de Zaragoza) ; Carmona, María ; Rodríguez, Ricardo ; Viguri, Fernando (Universidad de Zaragoza) ; Lahoz, Fernando J. ; García-Orduña, Pilar ; Carmona, Daniel

Resumen: An improved synthesis of the racemic rhodium compound [RhCl2(κ4C,N,N′,P-L1)] (1) containing an achiral tripodal tetradentate ligand is reported. Their derived solvate complexes [Rh(κ4C,N,N′,P-L1)(Solv)2][SbF6]2 (Solv = NCMe, 2; H2O, 3) are resolved into their two enantiomers. Complexes 2 and 3 catalyze the Diels–Alder (DA) reaction between methacrolein and cyclopentadiene and the 1,3-dipolar cycloaddition reaction between methacrolein and the nitrone N-benzylidenphenylamine-N-oxide. When enantiopure (ARh,RN)-2 was employed as the catalyst, enantiomeric ratios >99/1, in the R at C2 adduct, and up to 94/6, in the 3,5-endo isomer, were achieved in the DA reaction and in the 1,3-dipolar cycloaddition reaction, respectively. A plausible catalytic cycle that accounts for the origin of the observed enantioselectivity is proposed.

Idioma: Inglés

DOI: 10.1039/d2ra06982b

Año: 2022

Publicado en: RSC Advances 12, 53 (2022), 34704-34714
ISSN: 2046-2069

Factor impacto JCR: 3.9 (2022)

Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 74 / 178 = 0.416 (2022) - Q2 - T2

Factor impacto CITESCORE: 6.8 - Chemistry (Q1) - Chemical Engineering (Q2)

Factor impacto SCIMAGO: 0.678 - Chemistry (miscellaneous) (Q2) - Chemical Engineering (miscellaneous) (Q2)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E05-20R
Financiación: info:eu-repo/grantAgreement/ES/MCIU-AEI-FEDER/PID2021-122406NB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/CTQ2018-095561-BI00

Tipo y forma: Artículo (Versión definitiva)

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