000156591 001__ 156591
000156591 005__ 20251017144623.0
000156591 0247_ $$2doi$$a10.1002/adsc.202401458
000156591 0248_ $$2sideral$$a143853
000156591 037__ $$aART-2025-143853
000156591 041__ $$aeng
000156591 100__ $$0(orcid)0000-0002-3726-0493$$aAuria-Luna, Fernando
000156591 245__ $$aUnderstanding Chiral Proton Catalysis Using Cinchonium Derivatives in aza‐Michael Additions
000156591 260__ $$c2025
000156591 5060_ $$aAccess copy available to the general public$$fUnrestricted
000156591 5203_ $$aThis work presents a detailed mechanistic study of a quininium‐catalyzed aza‐Michael reaction, providing essential information for advancing chiral proton catalysis (CPC). The use of cinchona derivatives as chiral proton catalysts demonstrates their potential beyond their conventional roles as base‐promoted and phase‐transfer catalysts. Competitive reaction pathways are explored using density functional theory (DFT), wavefunction theory, and microkinetic simulations. Theoretical analyses are complemented with experimental titration and kinetic techniques to verify the intrinsic details of the reaction. This study reveals an intricate hydrogen bond network formed in the rate‐ and selectivity‐determining step, involving four noncovalently attached components that favor a stronger substrate⋅⋅⋅catalyst interaction in the R transition state. Significantly, this research emphasizes the pivotal role of carboxylate anions as nucleophile‐activating bases impacting reaction yield and enantioselectivity. Therefore, this work introduces cinchonium derivatives as new options for CPC and provides a thorough mechanistic analysis significant in expanding this underdeveloped catalytic domain.
000156591 536__ $$9info:eu-repo/grantAgreement/ES/AEI/PID2020-117455GB-I00$$9info:eu-repo/grantAgreement/ES/DGA/E07-23R$$9info:eu-repo/grantAgreement/ES/MICINN AEI/PID2022-136861NB-I00$$9info:eu-repo/grantAgreement/ES/MICINN/PID2022-140159NA-I00$$9info:eu-repo/grantAgreement/ES/MICINN/PID2023-147471NB-I00
000156591 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000156591 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000156591 700__ $$0(orcid)0000-0001-6832-8983$$aMarqués-López, Eugenia$$uUniversidad de Zaragoza
000156591 700__ $$0(orcid)0000-0003-0553-0695$$aGimeno, M. Concepción
000156591 700__ $$0(orcid)0000-0002-0769-7168$$aAlegre-Requena, Juan V.
000156591 700__ $$0(orcid)0000-0002-5244-9569$$aPérez Herrera, Raquel
000156591 7102_ $$12013$$2765$$aUniversidad de Zaragoza$$bDpto. Química Orgánica$$cÁrea Química Orgánica
000156591 773__ $$g367 (2025), e202401458 [8 pp.]$$pAdv. synth. catal.$$tAdvanced Synthesis and Catalysis$$x1615-4150
000156591 8564_ $$s1749882$$uhttps://zaguan.unizar.es/record/156591/files/texto_completo.pdf$$yPostprint
000156591 8564_ $$s2662941$$uhttps://zaguan.unizar.es/record/156591/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000156591 909CO $$ooai:zaguan.unizar.es:156591$$particulos$$pdriver
000156591 951__ $$a2025-10-17-14:22:37
000156591 980__ $$aARTICLE