doi:10.1039/d2ra06982bengTejero, Alvaro G.Carmona, MaríaRodríguez, RicardoViguri, FernandoLahoz, Fernando J.García-Orduña, PilarCarmona, DanielSynthesis of chiral-at-metal rhodium complexes from achiral tripodal tetradentate ligands: resolution and application to enantioselective Diels–Alder and 1,3-dipolar cycloadditionsART-2022-132734An 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.2022http://zaguan.unizar.es/record/12437910.1039/d2ra06982bhttp://zaguan.unizar.es/record/124379oai:zaguan.unizar.es:124379info:eu-repo/grantAgreement/ES/DGA/E05-20Rinfo:eu-repo/grantAgreement/ES/MCIU-AEI-FEDER/PID2021-122406NB-I00info:eu-repo/grantAgreement/ES/MICINN/CTQ2018-095561-BI00RSC Advances 12, 53 (2022), 34704-34714by-nchttp://creativecommons.org/licenses/by-nc/3.0/es/info:eu-repo/semantics/openAccess