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Article: Pillar[5]arene as a Co-factor in templating rotaxane formation

TitlePillar[5]arene as a Co-factor in templating rotaxane formation
Authors
Issue Date2013
Citation
Journal of the American Chemical Society, 2013, v. 135, n. 45, p. 17019-17030 How to Cite?
AbstractAfter the manner in which coenzymes often participate in the binding of substrates in the active sites of enzymes, pillar[5]arene, a macrocycle containing five hydroquinone rings linked through their para positions by methylene bridges, modifies the binding properties of cucurbit[6]uril, such that the latter templates azide-alkyne cycloadditions that do not occur in the presence of only the cucurbit[6]uril, a macrocycle composed of six glycoluril residues doubly linked through their nitrogen atoms to each other by methylene groups. Here, we describe how a combination of pillar[5]arene and cucurbit[6]uril interacts cooperatively with bipyridinium dications substituted on their nitrogen atoms with 2-azidoethyl- to 5-azidopentyl moieties to afford, as a result of orthogonal templation, two [4]rotaxanes and one [5]rotaxane in >90% yields inside 2 h at 55 C in acetonitrile. Since the hydroxyl groups on pillar[5]arene and the carbonyl groups on cucurbit[6]uril form hydrogen bonds readily, these two macrocycles work together in a cooperative fashion to the extent that the four conformational isomers of pillar[5]arene can be trapped on the dumbbell components of the [4]rotaxanes. In the case of the [5]rotaxane, it is possible to isolate a compound containing two pillar[5]arene rings with local C5 symmetries. In addition to fixing the stereochemistries of the pillar[5]arene rings, the regiochemistries associated with the 1,3-dipolar cycloadditions have been extended in their constitutional scope. Under mild conditions, orthogonal recognition motifs have been shown to lead to templation with positive cooperativity that is fast and all but quantitative, as well as being green and efficient. © 2013 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/333050
ISSN
2023 Impact Factor: 14.4
2023 SCImago Journal Rankings: 5.489
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorKe, Chenfeng-
dc.contributor.authorStrutt, Nathan L.-
dc.contributor.authorLi, Hao-
dc.contributor.authorHou, Xisen-
dc.contributor.authorHartlieb, Karel J.-
dc.contributor.authorMcGonigal, Paul R.-
dc.contributor.authorMa, Zhidong-
dc.contributor.authorIehl, Julien-
dc.contributor.authorStern, Charlotte L.-
dc.contributor.authorCheng, Chuyang-
dc.contributor.authorZhu, Zhixue-
dc.contributor.authorVermeulen, Nicolaas A.-
dc.contributor.authorMeade, Thomas J.-
dc.contributor.authorBotros, Youssry Y.-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-10-06T05:16:21Z-
dc.date.available2023-10-06T05:16:21Z-
dc.date.issued2013-
dc.identifier.citationJournal of the American Chemical Society, 2013, v. 135, n. 45, p. 17019-17030-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10722/333050-
dc.description.abstractAfter the manner in which coenzymes often participate in the binding of substrates in the active sites of enzymes, pillar[5]arene, a macrocycle containing five hydroquinone rings linked through their para positions by methylene bridges, modifies the binding properties of cucurbit[6]uril, such that the latter templates azide-alkyne cycloadditions that do not occur in the presence of only the cucurbit[6]uril, a macrocycle composed of six glycoluril residues doubly linked through their nitrogen atoms to each other by methylene groups. Here, we describe how a combination of pillar[5]arene and cucurbit[6]uril interacts cooperatively with bipyridinium dications substituted on their nitrogen atoms with 2-azidoethyl- to 5-azidopentyl moieties to afford, as a result of orthogonal templation, two [4]rotaxanes and one [5]rotaxane in >90% yields inside 2 h at 55 C in acetonitrile. Since the hydroxyl groups on pillar[5]arene and the carbonyl groups on cucurbit[6]uril form hydrogen bonds readily, these two macrocycles work together in a cooperative fashion to the extent that the four conformational isomers of pillar[5]arene can be trapped on the dumbbell components of the [4]rotaxanes. In the case of the [5]rotaxane, it is possible to isolate a compound containing two pillar[5]arene rings with local C5 symmetries. In addition to fixing the stereochemistries of the pillar[5]arene rings, the regiochemistries associated with the 1,3-dipolar cycloadditions have been extended in their constitutional scope. Under mild conditions, orthogonal recognition motifs have been shown to lead to templation with positive cooperativity that is fast and all but quantitative, as well as being green and efficient. © 2013 American Chemical Society.-
dc.languageeng-
dc.relation.ispartofJournal of the American Chemical Society-
dc.titlePillar[5]arene as a Co-factor in templating rotaxane formation-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ja407229h-
dc.identifier.pmid24059594-
dc.identifier.scopuseid_2-s2.0-84887778177-
dc.identifier.volume135-
dc.identifier.issue45-
dc.identifier.spage17019-
dc.identifier.epage17030-
dc.identifier.eissn1520-5126-
dc.identifier.isiWOS:000327103600044-

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