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dc.contributor.authorCiaccia, Mariaen
dc.contributor.authorNúñez-Villanueva, Diegoen
dc.contributor.authorHunter, Christopheren
dc.date.accessioned2019-06-20T23:31:55Z
dc.date.available2019-06-20T23:31:55Z
dc.date.issued2019-07en
dc.identifier.issn0002-7863
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/293824
dc.description.abstractCovalent templating provides an attractive solution to the controlled synthesis of linear oligomers, because a template oligomer can be used to define the precise length and sequence of the product. If the monomer units are attached to the template using kinetically inert covalent bonds, it should be possible to operate at high dilution to favour intramolecular over intermolecular reaction. However, for oligomerisation reactions using copper catalysed azide alkyne cycloaddition (CuAAC) this is not the case. The rate limiting step is formation of an activated copper complex, so any alkyne that is activated by copper reacts rapidly with the nearest available azide. As a result, every time a chain end alkyne is activated, rapid intermolecular reaction takes place with a different oligomer leading to the formation of higher order products. It proved possible to block these intermolecular reactions by adding an excess of an azide capping agent that intercepts the chain end of the growing oligomer on the template. By adjusting the concentration of the capping agent to compete effectively with the unwanted intermolecular reactions without interfering with the desired intramolecular reactions, it was possible to obtain quantitative yields of copy strands from covalent template-directed oligomerisation reactions. Remarkably the capping agent could also be used to control the stereochemistry of the duplex formed in the templated oligomerisation reaction to give exclusively the antiparallel product.
dc.description.sponsorshipERC-2012-AdG 320539-duplex, Herchel Smith Fund
dc.format.mediumPrint-Electronicen
dc.languageengen
dc.publisherAmerican Chemical Society
dc.rightsAll rights reserved
dc.subjectCopperen
dc.subjectAzidesen
dc.subjectAlkynesen
dc.subjectDimerizationen
dc.subjectKineticsen
dc.subjectCatalysisen
dc.subjectPolymerizationen
dc.subjectCycloaddition Reactionen
dc.titleCapping Strategies for Covalent Template-Directed Synthesis of Linear Oligomers Using CuAAC.en
dc.typeArticle
prism.endingPage10875
prism.issueIdentifier27en
prism.publicationDate2019en
prism.publicationNameJournal of the American Chemical Societyen
prism.startingPage10862
prism.volume141en
dc.identifier.doi10.17863/CAM.40937
dcterms.dateAccepted2019-06-13en
rioxxterms.versionofrecord10.1021/jacs.9b04973en
rioxxterms.versionAM
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserveden
rioxxterms.licenseref.startdate2019-07en
dc.contributor.orcidNúñez-Villanueva, Diego [0000-0002-1005-1464]
dc.contributor.orcidHunter, Christopher [0000-0002-5182-1859]
dc.identifier.eissn1520-5126
rioxxterms.typeJournal Article/Reviewen
pubs.funder-project-idEuropean Research Council (320539)
cam.orpheus.successThu Jan 30 10:43:10 GMT 2020 - Embargo updated*
rioxxterms.freetoread.startdate2020-07-31


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