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dc.contributor.authorChadda, Rekha
dc.contributor.authorMcArdle, Patrick
dc.contributor.authorMurphy, Paul V.
dc.date.accessioned2018-01-09T15:56:39Z
dc.date.issued2017-04-20
dc.identifier.citationChadda, Rekha, McArdle, Patrick, & Murphy, Paul V. (2017). Allylic Azide Rearrangement in Tandem with Intramolecular Huisgen Cycloaddition for Iminosugar and Glycomimetic Synthesis: Functionalized Piperidine, Pyrrolidine, and Pyrrolotriazoles from d-Mannose. Synthesis, 49(10), 2138-2152. doi: 10.1055/s-0036-1588791en_IE
dc.identifier.issn1437-210X
dc.identifier.urihttp://hdl.handle.net/10379/7083
dc.description.abstractIntramolecular Huisgen azide-alkene cycloaddition reaction of 7-azido-hepta-1,5-diene-3,4-diols, prepared from methyl α-d-man­no­pyranoside, were carried out. Allylic azide rearrangement to secondary azides occurred in tandem with triazoline formation and this intermediate was then decomposed in the presence of nucleophilic reagents to give pyrrolidines, piperidines, or azepanes depending on whether cyclic constraint was incorporated or not, on diol stereochemistry and on the nucleophile. The tandem reaction worked best when aziridine formation from the triazoline was efficient, and this efficiency improved on removal of cyclic constraint. Proposals to account for the observed diastereoselectivities are provided. The allylic azide rearrangement in tandem with the intramolecular Huisgen azide-alkyne cycloaddition was also investigated from azidoheptaenyne diols and gave dihydropyrrolotriazoles. All reactions were diastereoselective, and this was high in some cases. Two X-ray crystal structural determinations, 13C NMR data, and 1D and 2D NOESY experiments were used for stereochemical assignments.en_IE
dc.description.sponsorshipThe research was supported by NUI Galway (College of Science PhD scholarship to RC) and a Science Foundation Ireland IvP award to PVM (grant number 12/IA/1398 co-funded by the European Regional Development Fund under grant number 14/SP/2710).en_IE
dc.formatapplication/pdfen_IE
dc.language.isoenen_IE
dc.publisherThieme Publishingen_IE
dc.relation.ispartofSynthesisen
dc.rightsAttribution-NonCommercial-NoDerivs 3.0 Ireland
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/3.0/ie/
dc.subjectTandem reactionen_IE
dc.subjectAllylic azide rearrangementen_IE
dc.subjectAzide-alkene cycloadditionen_IE
dc.subjectStereoselective synthesisen_IE
dc.subjectIminosugaren_IE
dc.subjectGlycomimeticen_IE
dc.titleAllylic azide rearrangement in tandem with intramolecular Huisgen cycloaddition for iminosugar and glycomimetic synthesis. Functionalized piperidine, pyrrolidine and pyrrolotriazoles from D-mannoseen_IE
dc.typeArticleen_IE
dc.date.updated2018-01-05T09:06:59Z
dc.identifier.doi10.1055/s-0036-1588791
dc.local.publishedsourcehttp://dx.doi.org/10.1055/s-0036-1588791en_IE
dc.description.peer-reviewedpeer-reviewed
dc.description.embargo2018-04-20
dc.internal.rssid13695229
dc.local.contactPaul Murphy, School Of Chemistry, Room 236, Arts/Science Building, Nui Galway. 2465 Email: paul.v.murphy@nuigalway.ie
dc.local.copyrightcheckedNo
dc.local.versionACCEPTED
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