Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers

Handle URI:
http://hdl.handle.net/10754/624886
Title:
Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers
Authors:
Della Sala, Giorgio; Sicignano, Marina; Schettini, Rosaria; De Riccardis, Francesco; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Minenkov, Yury; Batisse, Chloé; Hanquet, Gilles; Leroux, Frederic; IZZO, Irene
Abstract:
The 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.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Della 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.
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Organic Chemistry
Issue Date:
31-May-2017
DOI:
10.1021/acs.joc.7b00743
Type:
Article
ISSN:
0022-3263; 1520-6904
Sponsors:
Financial 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.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.joc.7b00743
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorDella Sala, Giorgioen
dc.contributor.authorSicignano, Marinaen
dc.contributor.authorSchettini, Rosariaen
dc.contributor.authorDe Riccardis, Francescoen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorMinenkov, Yuryen
dc.contributor.authorBatisse, Chloéen
dc.contributor.authorHanquet, Gillesen
dc.contributor.authorLeroux, Fredericen
dc.contributor.authorIZZO, Ireneen
dc.date.accessioned2017-06-08T09:42:44Z-
dc.date.available2017-06-08T09:42:44Z-
dc.date.issued2017-05-31en
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.en
dc.identifier.issn0022-3263en
dc.identifier.issn1520-6904en
dc.identifier.doi10.1021/acs.joc.7b00743en
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.en
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.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.joc.7b00743en
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.en
dc.titleSwitchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethersen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalThe Journal of Organic Chemistryen
dc.eprint.versionPost-printen
dc.contributor.institutionDipartimento di Chimica e Biologia “A. Zambelli”, Università degli Studi di Salerno, Via Giovanni Paolo II 132, 84084 Fisciano (SA), Italyen
dc.contributor.institutionCNRS, Laboratoire de Chimie moléculaire UMR 7509 ECPM, Université de Strasbourg, 25 rue Becquerel, 67087 Strasbourg, Franceen
kaust.authorCavallo, Luigien
kaust.authorMinenkov, Yuryen
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