124379 20250210083428.0 doi 10.1039/d2ra06982b sideral 132734 ART-2022-132734 eng Tejero, Alvaro G. Universidad de Zaragoza Synthesis of chiral-at-metal rhodium complexes from achiral tripodal tetradentate ligands: resolution and application to enantioselective Diels–Alder and 1,3-dipolar cycloadditions 2022 Access copy available to the general public Unrestricted 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. info:eu-repo/grantAgreement/ES/DGA/E05-20R info:eu-repo/grantAgreement/ES/MCIU-AEI-FEDER/PID2021-122406NB-I00 info:eu-repo/grantAgreement/ES/MICINN/CTQ2018-095561-BI00 info:eu-repo/semantics/openAccess by-nc http://creativecommons.org/licenses/by-nc/3.0/es/ 3.9 2022 CHEMISTRY, MULTIDISCIPLINARY 74 / 178 = 0.416 2022 Q2 T2 0.678 2022 Chemistry (miscellaneous) 2022 Q2 Chemical Engineering (miscellaneous) 2022 Q2 6.8 2022 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Carmona, María Rodríguez, Ricardo (orcid)0000-0002-8845-0174 Viguri, Fernando Universidad de Zaragoza (orcid)0000-0002-6160-3046 Lahoz, Fernando J. (orcid)0000-0001-8054-2237 García-Orduña, Pilar Carmona, Daniel (orcid)0000-0003-4196-5856 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 12, 53 (2022), 34704-34714 RSC ADVANCES RSC Advances 2046-2069 1222651 http://zaguan.unizar.es/record/124379/files/texto_completo.pdf Versión publicada 2909885 http://zaguan.unizar.es/record/124379/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:124379 articulos driver 2025-02-10-08:31:19 ARTICLE