Enantioselective hydroformylation by a Rh-catalyst entrapped in a supramolecular metallocage
dc.contributor.author
dc.date.accessioned
2016-02-22T13:20:41Z
dc.date.available
2016-02-22T13:20:41Z
dc.date.issued
2015
dc.identifier.issn
0002-7863
dc.identifier.uri
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
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.)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
MICINN/PN 2010-2016/CSD2010-00065
MICINN/PN 2011/INP-2011-0059-PCT-420000
AGAUR/2009-2014/2009 SGR-637
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ja512637k
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© Journal of the American Chemical Society, 2015, vol. 137, p. 2680-2687
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Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
Enantioselective hydroformylation by a Rh-catalyst entrapped in a supramolecular metallocage
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.relation.projectID
info:eu-repo/grantAgreement/EC/FP7/277801/EU/Sustainable C-X and C-H Functionalization Catalyzed by Copper(III) Species/SUSCATCU3
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
dc.identifier.idgrec
022119
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-5126