{ "dc.contributor.author": "Gómez Martín, Laura" , "dc.contributor.author": "Canta i Roldós, Mercè" , "dc.contributor.author": "Font Gimbernat, David" , "dc.contributor.author": "Prat Casellas, Irene" , "dc.contributor.author": "Ribas Salamaña, Xavi" , "dc.contributor.author": "Costas Salgueiro, Miquel" , "dc.date.accessioned": "2015-03-24T07:50:20Z" , "dc.date.available": "2015-03-24T07:50:20Z" , "dc.date.issued": "2013" , "dc.identifier.issn": "0022-3263" , "dc.identifier.uri": "http://hdl.handle.net/10256/10179" , "dc.description.abstract": "Selective oxidation of alkyl C-H groups constitutes one of the highest challenges in organic synthesis. In this work, we show that mononuclear iron coordination complexes Lambda-[Fe(CF3SO3)(2)((S,S,R)-MCPP)] (Lambda-1P), Delta-[Fe(CF3SO3)(2)((R,R,R)-MCPP)] (Delta-1P), Lambda-[Fe(CF3SO3)(2)((S,S,R)-BPBPP)] (Lambda-2P), and Delta-[Fe(CF3SO3)(2)((R,R,R)-BPBPP)] (Delta-2P) catalyze the fast, efficient, and selective oxidation of nonactivated alkyl C-H groups employing H2O2 as terminal oxidant. These complexes are based on tetradentate N-based ligands and contain iron centers embedded in highly structured coordination sites defined by two bulky 4,5-pinenopyridine donor ligands, a chiral diamine ligand backbone, and chirality at the metal (Lambda or Delta). X-ray diffraction analysis shows that in Lambda-1P and Lambda-2P the pinene rings create cavity-like structures that isolate the iron site. The efficiency and regioselectivity in catalytic C-H oxidation reactions of these structurally rich complexes has been compared with those of Lambda-[Fe(CF3SO3)(2)((S,S)-MCP)] (Lambda-1), Lambda-[Fe(CF3SO3)(2)((S,S)-BPBP)] (Lambda-2), Delta-[Fe(CF3SO3)(2)((R,R)-BPBP)] (Delta-2), Lambda-[Fe(CH3CN)(2)((S,S)-BPBP)] (SbF6)(2) (Lambda-2SbF(6)), and Delta-[Fe(CH3CN)(2)((R,R)-BPBP)](SbF6)(2) (Delta-2SbF(6)), which lack the steric bulk introduced by the pinene rings. Cavity-containing complexes Lambda-1P and Lambda-2P exhibit enhanced activity in comparison with Delta-1P, Delta-2P, Lambda-1, Lambda-2, and Lambda-2SbF(6). The regioselectivity exhibited by catalysts Lambda-1P, Lambda-2P, Delta-1P, and Delta-2P in the C-H oxidation of simple organic molecules can be predicted on the basis of the innate properties of the distinct C-H groups of the substrate. However, in specific complex organic molecules where oxidation of multiple C-H sites is competitive, the highly elaborate structure of the catalysts allows modulation of C-H regioselectivity between the oxidation of tertiary and secondary C-H groups and also among multiple methylene sites, providing oxidation products in synthetically valuable yields. These selectivities complement those accomplished with structurally simpler oxidants, including non-heme iron catalysts Lambda-2 and Lambda-2SbF(6)" , "dc.description.sponsorship": "We thank the European Research Foundation for Starting Grant Project ERC-2009-StG-239910, MICINN for project CTQ2009-08464 and a Ph.D. grant (I.P.), and the Generalitat de Catalunya for a Ph.D. grant (M. Canta). X.R. thanks financial support from INNPLANTA project INP-2011-0059-PCT-420000-ACT1. M.C. and X.R. thank ICREA Academia Awards" , "dc.format.mimetype": "application/pdf" , "dc.language.iso": "eng" , "dc.publisher": "American Chemical Society (ACS)" , "dc.relation": "MICINN/PN 2010-2012/CTQ2009-08464" , "dc.relation": "MICINN/PN 2011/INP-2011-0059-PCT-420000" , "dc.relation.isformatof": "Reproducció digital del document publicat a: http://dx.doi.org/ 10.1021/jo302196q" , "dc.relation.ispartof": "© Journal of Organic Chemistry, 2013, vol. 78, p. 1421-1433" , "dc.relation.ispartofseries": "Articles publicats (D-Q)" , "dc.rights": "Tots els drets reservats" , "dc.subject": "Oxidació" , "dc.subject": "Oxidation" , "dc.subject": "Catàlisi" , "dc.subject": "Catalysis" , "dc.subject": "Aigua oxigenada" , "dc.subject": "Hydrogen peroxide" , "dc.subject": "Ferro" , "dc.subject": "Iron" , "dc.title": "Regioselective oxidation of nonactivated alkyl C-H groups using highly structured non-heme iron catalysts" , "dc.type": "info:eu-repo/semantics/article" , "dc.rights.accessRights": "info:eu-repo/semantics/embargoedAccess" , "dc.embargo.terms": "Cap" , "dc.relation.projectID": "info:eu-repo/grantAgreement/EC/FP7/239910/EU/Bio-inspired Design of Catalysts for Selective Oxidations of C-H and C=C Bonds/BIDECASEOX" , "dc.type.version": "info:eu-repo/semantics/publishedVersion" , "dc.identifier.doi": "http://dx.doi.org/ 10.1021/jo302196q" , "dc.identifier.idgrec": "018648" , "dc.contributor.funder": "Ministerio de Ciencia e Innovación (Espanya)" , "dc.relation.FundingProgramme": "FP7" , "dc.relation.ProjectAcronym": "BIDECASEOX" , "dc.identifier.eissn": "1520-6904" }