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Enantioselective hydroformylation by a Rh-catalyst entrapped in a supramolecular metallocage

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dc.contributor.author García Simón, Cristina
dc.contributor.author Gramage Doria, Rafael
dc.contributor.author Raoufmoghaddam, Saeed
dc.contributor.author Parella Coll, Teodor
dc.contributor.author Costas Salgueiro, Miquel
dc.contributor.author Ribas Salamaña, Xavi
dc.contributor.author Reek, Joost N.H.
dc.date.issued 2015
dc.identifier.issn 0002-7863 (versió paper)
dc.identifier.issn 1520-5126 (versió electrònica)
dc.identifier.uri http://hdl.handle.net/10256/12117
dc.description.abstract Regio- and enantioselective hydroformylation of styrenes is attained upon embedding a chiral Rh complex in a nonchiral supramolecular cage formed from coordination-driven self-assembly of macrocyclic dipalladium complexes and tetracarboxylate zinc porphyrins. The resulting supramolecular catalyst converts styrene derivatives into aldehyde products with much higher chiral induction in comparison to the nonencapsulated Rh catalyst. Spectroscopic analysis shows that encapsulation does not change the electronic properties of the catalyst nor its first coordination sphere. Instead, enhanced enantioselectivity is rationalized by the modification of the second coordination sphere occurring upon catalyst inclusion inside the cage, being one of the few examples in achieving an enantioselective outcome via indirect through-space control of the chirality around the catalyst center. This effect resembles those taking place in enzymatic sites, where structural constraints imposed by the enzyme cavity can impart stereoselectivities that cannot be attained in bulk. These results are a showcase for the future development of asymmetric catalysis by using size-tunable supramolecular capsules cat
dc.description.sponsorship We thank the European Research Council (ERC-2011-StG- 277801 to X.R., ERC-2009-StG-239910 to M.C., and ERC- 2013-AdG-339782-NAT_CAT to J.N.H.R.), the Spanish MINECO (Consolider-Ingenio CSD2010-00065, INNPLANTA project INP-2011-0059-PCT-420000-ACT1, and CTQ2012-32436), and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637 and PhD grant to C.G.S.) cat
dc.format.mimetype application/pdf cat
dc.language.iso eng cat
dc.publisher American Chemical Society (ACS) cat
dc.relation MICINN/PN 2010-2016/CSD2010-00065 cat
dc.relation MICINN/PN 2011/INP-2011-0059-PCT-420000 cat
dc.relation AGAUR/2009-2014/2009 SGR-637 cat
dc.relation.isformatof Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ja512637k cat
dc.relation.ispartof © Journal of the American Chemical Society, 2015, vol. 137, p. 2680-2687 cat
dc.relation.ispartofseries Articles publicats (D-Q) cat
dc.rights Tots els drets reservats cat
dc.subject Catalitzadors de rodi cat
dc.subject Rhodium catalyst cat
dc.title Enantioselective hydroformylation by a Rh-catalyst entrapped in a supramolecular metallocage cat
dc.type info:eu-repo/semantics/article cat
dc.rights.accessRights info:eu-repo/semantics/closedAccess cat
dc.embargo.terms Cap cat
dc.relation.projectID info:eu-repo/grantAgreement/EC/FP7/277801 cat
dc.relation.projectID info:eu-repo/grantAgreement/EC/FP7/239910 cat
dc.type.version info:eu-repo/semantics/publishedVersion cat
dc.identifier.doi http://dx.doi.org/10.1021/ja512637k
dc.contributor.funder Ministerio de Ciencia e Innovación (Espanya) cat
dc.contributor.funder Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recerca cat

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