Please use this identifier to cite or link to this item: http://hdl.handle.net/2440/113442
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dc.contributor.authorHuxley, M.en
dc.contributor.authorBurgun, A.en
dc.contributor.authorGhodrati, H.en
dc.contributor.authorCoghlan, C.en
dc.contributor.authorLemieux, A.en
dc.contributor.authorChampness, N.en
dc.contributor.authorHuang, D.en
dc.contributor.authorDoonan, C.en
dc.contributor.authorSumby, C.en
dc.date.issued2018en
dc.identifier.citationJournal of the American Chemical Society, 2018; 140(20):6416-6425en
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.urihttp://hdl.handle.net/2440/113442-
dc.description.abstractSite-selective organic transformations are commonly required in the synthesis of complex molecules. By employing a bespoke metal-organic framework (MOF, 1·[Mn(CO)3N3]), in which coordinated azide anions are precisely positioned within 1D channels, we present a strategy for the site-selective transformation of dialkynes into alkyne-functionalized triazoles. As an illustration of this approach, 1,7-octadiyne-3,6-dione stoichiometrically furnishes the mono-"click" product N-methyl-4-hex-5'-ynl-1',4'-dione-1,2,3-triazole with only trace bis-triazole side-product. Stepwise insights into conversions of the MOF reaction vessel were obtained by X-ray crystallography, demonstrating that the reactive sites are "isolated" from one another. Single-crystal to single-crystal transformations of the Mn(I)-metalated material 1·[Mn(CO)3(H2O)]Br to the corresponding azide species 1·[Mn(CO)3N3] with sodium azide, followed by a series of [3+2] azide-alkyne cycloaddition reactions, are reported. The final liberation of the "click" products from the porous material is achieved by N-alkylation with MeBr, which regenerates starting MOF 1·[Mn(CO)3(H2O)]Br and releases the organic products, as characterized by NMR spectroscopy and mass spectrometry. Once the dialkyne length exceeds the azide separation, site selectivity is lost, confirming the critical importance of isolated azide moieties for this strategy. We postulate that carefully designed MOFs can act as physical protecting groups to facilitate other site-selective and chemoselective transformations.en
dc.description.statementofresponsibilityMichael. T. Huxley, Alexandre Burgun, Hanieh Ghodrati, Campbell J. Coghlan, Anthony Lemieux, Neil R. Champness, David M. Huang, Christian J. Doonan, and Christopher J. Sumbyen
dc.language.isoenen
dc.publisherACS Publicationsen
dc.rights© 2018 American Chemical Societyen
dc.titleProtecting-group-free site-selective reactions in a metal-organic framework reaction vesselen
dc.typeJournal articleen
dc.identifier.rmid0030086590en
dc.identifier.doi10.1021/jacs.8b02896en
dc.relation.granthttp://purl.org/au-research/grants/arc/DP160103234en
dc.identifier.pubid419065-
pubs.library.collectionChemistry publicationsen
pubs.library.teamDS05en
pubs.verification-statusVerifieden
pubs.publication-statusPublisheden
dc.identifier.orcidGhodrati, H. [0000-0002-4954-9892]en
dc.identifier.orcidCoghlan, C. [0000-0003-1625-3216]en
dc.identifier.orcidHuang, D. [0000-0003-2048-4500]en
dc.identifier.orcidSumby, C. [0000-0002-9713-9599]en
Appears in Collections:Chemistry publications

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