Metal-organic frameworks invert molecular reactivity: Lewis acidic phosphonium zwitterions catalyze the Aldol-Tishchenko reaction.

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dc.contributor.authorBauer, Gerald
dc.contributor.authorOngari, Daniele
dc.contributor.authorXu, Xiaoying
dc.contributor.authorTiana, Davide
dc.contributor.authorSmit, Berend
dc.contributor.authorRanocchiari, Marco
dc.contributor.funderH2020 European Research Councilen
dc.contributor.funderNational Center of Competence in Research Materials’ Revolution: Computational Design and Discovery of Novel Materialsen
dc.contributor.funderSchweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschungen
dc.date.accessioned2018-01-04T16:51:21Z
dc.date.available2018-01-04T16:51:21Z
dc.date.issued2017-12-03
dc.date.updated2018-01-04T16:39:27Z
dc.description.abstractThe influence of metal–organic frameworks (MOFs) as additives is herein described for the reaction of n-alkyl aldehydes in the presence of methylvinylketone and triphenylphosphine. In the absence of a MOF, the expected Morita–Baylis–Hillman product, a β-hydroxy enone, is observed. In the presence of MOFs with UMCM-1 and MOF-5 topologies, the reaction is selective to Aldol-Tishchenko products, the 1 and 3 n-alkylesters of 2-alkyl-1,3-diols, which is unprecedented in organocatalysis. The (3-oxo-2-butenyl)triphenylphosphonium zwitterion, a commonly known nucleophile, is identified as the catalytic active species. This zwitterion favors nucleophilic character in solution, whereas once confined within the framework, it becomes an electrophile yielding Aldol-Tishchenko selectivity. Computational investigations reveal a structural change in the phosphonium moiety induced by the steric confinement of the framework that makes it accessible and an electrophile.en
dc.description.sponsorshipSwiss National Supercomputing Centre, CSCS (Project no. s611);en
dc.description.statusPeer revieweden
dc.description.versionPublished Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationBauer, G., Ongari, D., Xu, X., Tiana, D., Smit, B. and Ranocchiari, M. (2017) 'Metal–Organic Frameworks Invert Molecular Reactivity: Lewis Acidic Phosphonium Zwitterions Catalyze the Aldol-Tishchenko Reaction', Journal of the American Chemical Society, 139(50), pp. 18166-18169. doi:10.1021/jacs.7b10928en
dc.identifier.doi10.1021/jacs.7b10928
dc.identifier.endpage18169en
dc.identifier.issn1520-5126
dc.identifier.journaltitleJournal of the American Chemical Societyen
dc.identifier.startpage18166en
dc.identifier.urihttps://hdl.handle.net/10468/5235
dc.identifier.volume139en
dc.language.isoenen
dc.publisherAmerican Chemical Societyen
dc.relation.projectinfo:eu-repo/grantAgreement/EC/H2020::ERC::ERC-ADG/666983/EU/The Materials Genome in Action/MaGicen
dc.rights© 2017 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.en
dc.rights.urihttp://pubs.acs.org/page/policy/authorchoice_termsofuse.htmlen
dc.subjectMetal–organic frameworksen
dc.subjectAldol-Tishchenkoen
dc.subjectMOFsen
dc.subjectPhosphoniumen
dc.subjectMorita−Baylis−Hillman (MBH) reactionen
dc.titleMetal-organic frameworks invert molecular reactivity: Lewis acidic phosphonium zwitterions catalyze the Aldol-Tishchenko reaction.en
dc.typeArticle (peer-reviewed)en
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