{ "dc.contributor.author": "Vicens Serra, Laia" , "dc.contributor.author": "Olivo, Giorgio" , "dc.contributor.author": "Costas Salgueiro, Miquel" , "dc.date.accessioned": "2022-01-21T09:30:35Z" , "dc.date.available": "2022-01-21T09:30:35Z" , "dc.date.issued": "2022-02-07" , "dc.identifier.issn": "1433-7851" , "dc.identifier.uri": "http://hdl.handle.net/10256/20447" , "dc.description.abstract": "Precise delivery of a proton plays a key role in O2 activation at iron oxygenases, enabling the crucial O−O cleavage step that generates the oxidizing high-valent metal–oxo species. Such a proton is delivered by acidic residues that may either directly bind the iron center or lie in its second coordination sphere. Herein, a supramolecular strategy for enzyme-like H2O2 activation at a biologically inspired manganese catalyst, with a nearly stoichiometric amount (1–1.5 equiv) of a carboxylic acid is disclosed. Key for this strategy is the incorporation of an α,ω-amino acid in the second coordination sphere of a chiral catalyst via remote ammonium-crown ether recognition. The properly positioned carboxylic acid function enables effective activation of hydrogen peroxide, leading to catalytic asymmetric epoxidation. Modulation of both amino acid and catalyst structure can tune the efficiency and the enantioselectivity of the reaction, and a study on the oxidative degradation pathway of the system is presented" , "dc.description.sponsorship": "We acknowledge STR of UdG for experimental support.This work was supportedby Spanish Ministry of Science,Innovation and Universities (PGC2018-101737-B-I00 to M.C., J.d.C. grant FJCI-2016-30243 to G.O.and PhD grant FPU16/04231to L.V.) and Generalitat de Catalunya (ICREA Academia Awardto M.C.and 2014SGR 862)" , "dc.description.sponsorship": "Open Access funding provided thanks to the CRUE-CSIC agreement with Wiley" , "dc.format.mimetype": "application/pdf" , "dc.language.iso": "eng" , "dc.publisher": "Wiley" , "dc.relation": "PGC2018-101737-B-I00" , "dc.relation.isformatof": "Reproducció digital del document publicat a: https://doi.org/10.1002/anie.202114932" , "dc.relation.ispartof": "Angewandte Chemie International Edition, 2022, vol. 61, núm. 7, p. e202114932" , "dc.relation.ispartofseries": "Articles publicats (D-Q)" , "dc.rights": "Attribution 4.0 International" , "dc.rights.uri": "http://creativecommons.org/licenses/by/4.0/" , "dc.subject": "Catàlisi asimètrica" , "dc.subject": "Catalyse asymétrique" , "dc.subject": "Aminoàcids" , "dc.subject": "Amino acids" , "dc.title": "Remote Amino Acid Recognition Enables Effective Hydrogen Peroxide Activation at a Manganese Oxidation Catalyst" , "dc.type": "info:eu-repo/semantics/article" , "dc.rights.accessRights": "info:eu-repo/semantics/openAccess" , "dc.relation.projectID": "info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-101737-B-I00/ES/CATALISIS DE OXIDACION BIOINSPIRADA MEDIANTE DISEÑO RACIONAL DE CATALIZADORES/" , "dc.type.version": "info:eu-repo/semantics/publishedVersion" , "dc.identifier.doi": "https://doi.org/10.1002/anie.202114932" , "dc.identifier.idgrec": "034460" , "dc.contributor.funder": "Agencia Estatal de Investigación" , "dc.type.peerreviewed": "peer-reviewed" , "dc.relation.FundingProgramme": "Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020" , "dc.relation.ProjectAcronym": "CATALISIS DE OXIDACION BIOINSPIRADA MEDIANTE DISEÑO RACIONAL DE CATALIZADORES" , "dc.identifier.eissn": "1521-3773" }