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dc.contributor.authorLoke, Inga
dc.contributor.authorBentzinger, Guillaume
dc.contributor.authorHolz, Julia
dc.contributor.authorRaja, Aruna
dc.contributor.authorBhasin, Aman
dc.contributor.authorSasse, Florenz
dc.contributor.authorKöhn, Andreas
dc.contributor.authorSchobert, Rainer
dc.contributor.authorLaschat, Sabine
dc.date.accessioned2018-02-16T09:07:56Z
dc.date.available2018-02-16T09:07:56Z
dc.date.issued2016-01-21
dc.identifier.citationSynthesis of the AB ring system of clifednamide utilizing Claisen rearrangement and Diels-Alder reaction as key steps. 2016, 14 (3):884-94 Org. Biomol. Chem.en
dc.identifier.issn1477-0539
dc.identifier.pmid26599642
dc.identifier.doi10.1039/c5ob01491c
dc.identifier.urihttp://hdl.handle.net/10033/621282
dc.description.abstractIn order to construct the functionalized AB ring system of clifednamide, member of the class of macrocyclic tetramic acid lactams, a synthesis was developed which utilized an Ireland-Claisen rearrangement and an intramolecular Diels-Alder reaction. Starting from di-O-isopropylidene-d-mannitol the allyl carboxylate precursor for the sigmatropic rearrangement was prepared. This rearrangement proceeded diastereoselectively only in the presence of an allyl silyl ether instead of the parent enone in the side chain, as suggested by deuteration experiments. A subsequent Diels-Alder reaction yielded the target ethyl hexahydro-1H-indene-carboxylate with high diastereoselectivity. Quantum-chemical investigations of this intramolecular Diels-Alder reaction support the proposed configuration of the final product.
dc.language.isoenen
dc.rights.urihttp://creativecommons.org/licenses/by-nc-sa/4.0/*
dc.subject.meshCycloaddition Reactionen
dc.subject.meshHeterocyclic Compounds, 4 or More Ringsen
dc.subject.meshMannitolen
dc.subject.meshMolecular Structureen
dc.subject.meshPyrrolidinonesen
dc.subject.meshQuantum Theoryen
dc.subject.meshStereoisomerismen
dc.titleSynthesis of the AB ring system of clifednamide utilizing Claisen rearrangement and Diels-Alder reaction as key steps.en
dc.typeArticleen
dc.contributor.departmentHelmholtz-Zentrum für Infektionsforschung GmbH, Inhoffenstr. 7, 38124 Braunschweig, Germany.en
dc.identifier.journalOrganic & biomolecular chemistryen
refterms.dateFOA2018-06-12T19:57:59Z
html.description.abstractIn order to construct the functionalized AB ring system of clifednamide, member of the class of macrocyclic tetramic acid lactams, a synthesis was developed which utilized an Ireland-Claisen rearrangement and an intramolecular Diels-Alder reaction. Starting from di-O-isopropylidene-d-mannitol the allyl carboxylate precursor for the sigmatropic rearrangement was prepared. This rearrangement proceeded diastereoselectively only in the presence of an allyl silyl ether instead of the parent enone in the side chain, as suggested by deuteration experiments. A subsequent Diels-Alder reaction yielded the target ethyl hexahydro-1H-indene-carboxylate with high diastereoselectivity. Quantum-chemical investigations of this intramolecular Diels-Alder reaction support the proposed configuration of the final product.


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