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Article: Template-directed synthesis of multiply mechanically interlocked molecules under thermodynamic control

TitleTemplate-directed synthesis of multiply mechanically interlocked molecules under thermodynamic control
Authors
KeywordsDynamic covalent chemistry
Imine formation
Molecular recognition
Noncovalent interactions
Reductive amination
Issue Date2005
Citation
Chemistry - A European Journal, 2005, v. 11, n. 16, p. 4655-4666 How to Cite?
AbstractThe template-directed construction of crown-ether-like macrocycles around secondary dialkylammonium ions (R2NH2+) has been utilized for the expedient (one-pot) and high-yielding synthesis of a diverse range of mechanically interlocked molecules. The clipping together of appropriately designed dialdehyde and diamine compounds around R 2NH2+-containing dumbbell-shaped components proceeds through the formation, under thermodynamic control, of imine bonds. The reversible nature of this particular reaction confers the benefits of "error-checking" and "proof-reading", which one usually associates with supramolecular chemistry and strict self-assembly processes, upon these wholly molecular systems. Furthermore, these dynamic covalent syntheses exploit the efficient templating effects that the R2NH 2+ ions exert on the macrocyclization of the matched dialdehyde and diamine fragments, resulting not only in rapid rates of reaction, but also affording near-quantitative conversion of starting materials into the desired interlocked products. Once assembled, these "dynamic" interlocked compounds can be "fixed" upon reduction of the reversible imine bonds (by using BH3·THF) to give kinetically stable species, a procedure that can be performed in the same reaction vessel as the inital thermodynamically controlled assembly. Isolation and purification of the mechanically interlocked products formed by using this protocol is relatively facile, as no column chromatography is required. Herein, we present the synthesis and characterization of 1) a [2]rotaxane, 2) a [3]rotaxane, 3) a branched [4]rotaxane, 4) a bis [2]rotaxane, and 5) a novel cyclic [4]rotaxane, demonstrating, in incrementally more complex systems, the efficacy of this one-pot strategy for the construction of interlocked molecules. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Persistent Identifierhttp://hdl.handle.net/10722/332620
ISSN
2023 Impact Factor: 3.9
2023 SCImago Journal Rankings: 1.058
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorAricó, Fabio-
dc.contributor.authorChang, Theresa-
dc.contributor.authorCantrill, Stuart J.-
dc.contributor.authorKhan, Saeed I.-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-10-06T05:12:56Z-
dc.date.available2023-10-06T05:12:56Z-
dc.date.issued2005-
dc.identifier.citationChemistry - A European Journal, 2005, v. 11, n. 16, p. 4655-4666-
dc.identifier.issn0947-6539-
dc.identifier.urihttp://hdl.handle.net/10722/332620-
dc.description.abstractThe template-directed construction of crown-ether-like macrocycles around secondary dialkylammonium ions (R2NH2+) has been utilized for the expedient (one-pot) and high-yielding synthesis of a diverse range of mechanically interlocked molecules. The clipping together of appropriately designed dialdehyde and diamine compounds around R 2NH2+-containing dumbbell-shaped components proceeds through the formation, under thermodynamic control, of imine bonds. The reversible nature of this particular reaction confers the benefits of "error-checking" and "proof-reading", which one usually associates with supramolecular chemistry and strict self-assembly processes, upon these wholly molecular systems. Furthermore, these dynamic covalent syntheses exploit the efficient templating effects that the R2NH 2+ ions exert on the macrocyclization of the matched dialdehyde and diamine fragments, resulting not only in rapid rates of reaction, but also affording near-quantitative conversion of starting materials into the desired interlocked products. Once assembled, these "dynamic" interlocked compounds can be "fixed" upon reduction of the reversible imine bonds (by using BH3·THF) to give kinetically stable species, a procedure that can be performed in the same reaction vessel as the inital thermodynamically controlled assembly. Isolation and purification of the mechanically interlocked products formed by using this protocol is relatively facile, as no column chromatography is required. Herein, we present the synthesis and characterization of 1) a [2]rotaxane, 2) a [3]rotaxane, 3) a branched [4]rotaxane, 4) a bis [2]rotaxane, and 5) a novel cyclic [4]rotaxane, demonstrating, in incrementally more complex systems, the efficacy of this one-pot strategy for the construction of interlocked molecules. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.-
dc.languageeng-
dc.relation.ispartofChemistry - A European Journal-
dc.subjectDynamic covalent chemistry-
dc.subjectImine formation-
dc.subjectMolecular recognition-
dc.subjectNoncovalent interactions-
dc.subjectReductive amination-
dc.titleTemplate-directed synthesis of multiply mechanically interlocked molecules under thermodynamic control-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/chem.200500148-
dc.identifier.scopuseid_2-s2.0-23744481517-
dc.identifier.volume11-
dc.identifier.issue16-
dc.identifier.spage4655-
dc.identifier.epage4666-
dc.identifier.isiWOS:000231324200008-

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