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dc.contributor.authorDella Sala, Giorgio
dc.contributor.authorSicignano, Marina
dc.contributor.authorSchettini, Rosaria
dc.contributor.authorDe Riccardis, Francesco
dc.contributor.authorCavallo, Luigi
dc.contributor.authorMinenkov, Yury
dc.contributor.authorBatisse, Chloé
dc.contributor.authorHanquet, Gilles
dc.contributor.authorLeroux, Frederic
dc.contributor.authorIZZO, Irene
dc.date.accessioned2017-06-08T09:42:44Z
dc.date.available2017-06-08T09:42:44Z
dc.date.issued2017-06-13
dc.identifier.citationDella Sala G, Sicignano M, Schettini R, De Riccardis F, Cavallo L, et al. (2017) Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers. The Journal of Organic Chemistry. Available: http://dx.doi.org/10.1021/acs.joc.7b00743.
dc.identifier.issn0022-3263
dc.identifier.issn1520-6904
dc.identifier.pmid28561585
dc.identifier.doi10.1021/acs.joc.7b00743
dc.identifier.urihttp://hdl.handle.net/10754/624886
dc.description.abstractThe fluoride promoted vinylogous Mukaiyama-Michael reaction (VMMR) of 2-trimethylsilyloxyfuran with diverse α,β-unsaturated ketones is described. The TBAF catalyzed VMMR afforded high anti-diastereoselectivity irrespective of the solvents used. The KF/crown ethers catalytic systems proved to be highly efficient in terms of yields and resulted in a highly diastereoselective unprecedented solvent/catalyst switchable reaction. Anti-adducts were obtained as single diastereomers or with excellent diastereoselectivities when benzo-15-crown-5 in CH2Cl2 was employed. On the other hand, high syn-diastereoselectivities (from 76:24 to 96:4) were achieved by employing dicyclohexane-18-crown-6 in toluene. Based on DFT calculations, the catalysts/solvents-dependent switchable diastereoselectivities are proposed to be the result of loose or tight cation-dienolate ion pairs.
dc.description.sponsorshipFinancial support from the University of Salerno (FARB) and Regione Campania under POR Campania FESR 2007-2013 – O.O. 2.1 (Farma-BioNet). We thank Dr. Patrizia Iannece for HRMS. Gilles Hanquet and Frédéric Leroux thank the CNRS (Centre National de la Recherche Scientifique, France). Chloé Batisse is very grateful to the IcFRC (International Center for Frontier Research in Chemistry), grant Cyclo-CF2-ASYM. Luigi Cavallo thanks the King Abdullah University of Science and technology for supporting this work. Computing resources used within this project have been provided by the KAUST Supercomputing Laboratory and by CRESCO/ENEAGRID High Performance Computing infrastructure and its staff.
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.joc.7b00743
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Organic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.joc.7b00743.
dc.titleSwitchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Division
dc.identifier.journalThe Journal of Organic Chemistry
dc.eprint.versionPost-print
dc.contributor.institutionDipartimento di Chimica e Biologia “A. Zambelli”, Università degli Studi di Salerno, Via Giovanni Paolo II 132, 84084 Fisciano (SA), Italy
dc.contributor.institutionCNRS, Laboratoire de Chimie moléculaire UMR 7509 ECPM, Université de Strasbourg, 25 rue Becquerel, 67087 Strasbourg, France
kaust.personCavallo, Luigi
kaust.personMinenkov, Yury
refterms.dateFOA2018-05-31T00:00:00Z
dc.date.published-online2017-06-13
dc.date.published-print2017-07-07


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