000163737 001__ 163737
000163737 005__ 20251121145033.0
000163737 0247_ $$2doi$$a10.1002/chem.202502858
000163737 0248_ $$2sideral$$a145810
000163737 037__ $$aART-2025-145810
000163737 041__ $$aeng
000163737 100__ $$0(orcid)0000-0003-4249-6748$$aPedrón, Manuel$$uUniversidad de Zaragoza
000163737 245__ $$aUnraveling the Ruthenium(VIII)-Mediated Oxidation of N-Hydroxy Pyrrolidines to Cyclic Nitrones
000163737 260__ $$c2025
000163737 5060_ $$aAccess copy available to the general public$$fUnrestricted
000163737 5203_ $$aThe oxidation of N‐hydroxypyrrolidines to cyclic nitrones represents a valuable transformation in organic synthesis due to the synthetic utility of such nitrones. In this work, we present a detailed computational study of the oxidation of five‐membered N‐hydroxylamines using ruthenium tetroxide. Through density functional theory (DFT) calculations complemented by topological analyses of the electron localization function (ELF), we reveal a concerted yet highly asynchronous two‐electron transfer mechanism. No intermediates as energy minima are identified, but the reaction trajectory lies near the borderline between stepwise and concerted pathways. Our findings indicate that regioselectivity in the oxidation process does not correlate with the electronic nature of the substituent at position 3, but is instead governed by steric hindrance effects that modulate the approach of the ruthenium tetroxide moiety. This steric control provides a rational explanation for the modest regioselectivity observed experimentally. Notably, the computational predictions align closely with experimental product distributions, lending strong support to the proposed mechanistic model.
000163737 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E34-20R$$9info:eu-repo/grantAgreement/ES/MICINN/PID2022-137973NB-I00
000163737 540__ $$9info:eu-repo/semantics/embargoedAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000163737 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000163737 700__ $$0(orcid)0000-0003-3433-6701$$aTejero, Tomás$$uUniversidad de Zaragoza
000163737 700__ $$0(orcid)0000-0002-2202-3460$$aMerino, Pedro$$uUniversidad de Zaragoza
000163737 7102_ $$12013$$2765$$aUniversidad de Zaragoza$$bDpto. Química Orgánica$$cÁrea Química Orgánica
000163737 773__ $$g(2025), e02858 [9 p.]$$pChemistry (Weinh.)$$tChemistry - A European Journal$$x0947-6539
000163737 8564_ $$s1362260$$uhttps://zaguan.unizar.es/record/163737/files/texto_completo.pdf$$yPostprint$$zinfo:eu-repo/date/embargoEnd/2026-09-30
000163737 8564_ $$s2322899$$uhttps://zaguan.unizar.es/record/163737/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint$$zinfo:eu-repo/date/embargoEnd/2026-09-30
000163737 909CO $$ooai:zaguan.unizar.es:163737$$particulos$$pdriver
000163737 951__ $$a2025-11-21-14:41:07
000163737 980__ $$aARTICLE