Synthesis of chiral-at-metal rhodium complexes from achiral tripodal tetradentate ligands: resolution and application to enantioselective Diels–Alder and 1,3-dipolar cycloadditions
| العنوان: | Synthesis of chiral-at-metal rhodium complexes from achiral tripodal tetradentate ligands: resolution and application to enantioselective Diels–Alder and 1,3-dipolar cycloadditions |
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| المؤلفون: | Alvaro G. Tejero, María Carmona, Ricardo Rodríguez, Fernando Viguri, Fernando J. Lahoz, Pilar García-Orduña, Daniel Carmona |
| المساهمون: | Ministerio de Ciencia, Innovación y Universidades (España), Agencia Estatal de Investigación (España), European Commission, Gobierno de Aragón |
| سنة النشر: | 2022 |
| مصطلحات موضوعية: | General Chemical Engineering, General Chemistry |
| الوصف: | 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. We thank the Ministerio de Ciencia, Innovación y Universidades (MCIU) of Spain, Agencia Estatal de Investigación (AEI) of Spain, Fondo Europeo de Desarrollo Regional (FEDER) (CTQ2018-095561-BI00 and PID2021-122406NB-I00) and Gobierno de Aragón (Grupo de Referencia: Catálisis Homogénea Enantioselectiva E05-20R) for financial support. |
| وصف الملف: | application/pdf |
| اللغة: | English |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::ea143274d3dfc893b7400af1fb1e4dd5 http://zaguan.unizar.es/record/124379 |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.doi.dedup.....ea143274d3dfc893b7400af1fb1e4dd5 |
| قاعدة البيانات: | OpenAIRE |
| الوصف غير متاح. |