Show simple item record

dc.contributor.authorGody, Guillaumeen
dc.contributor.authorRoberts, Derricken
dc.contributor.authorMaschmeyer, Thomasen
dc.contributor.authorPerrier, Sebastienen
dc.date.accessioned2016-05-27T10:16:13Z
dc.date.available2016-05-27T10:16:13Z
dc.date.issued2016-02-29en
dc.identifier.issn0002-7863
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/256102
dc.description.abstractClick reactions have provided access to an array of remarkably complex polymer architectures. However, the term “click” is often applied inaccurately to polymer ligation reactions that fail to respect the criteria that typify a true “click” reaction. With the purpose of providing a universal way to benchmark polymer−polymer coupling efficiency at equimolarity and thus evaluate the fulfilment of click criteria, we report a simple one-pot methodology involving the homodicoupling of α-end-functionalized polymers using a small-molecule bifunctional linker. A combination of SEC analysis and chromatogram deconvolution enables straightforward quantification of the coupling efficiency. We subsequently employ this methodology to evaluate an overlooked candidate for the click reaction family: the addition of primary amines to α-tertiary isocyanates (α- t NCO). Using our bifunctional linker coupling strategy, we show that the amine−t NCO reaction fulfills the criteria for a polymer−polymer click reaction, achieving rapid, chemoselective, and quantitative coupling at room temperature without generating any byproducts. We demonstrate that amine−t NCO coupling is faster and more efficient than the more common amine−tertiary active ester coupling under equivalent conditions. Additionally, we show that the α-tNCO end group is unprecedentedly stable in aqueous media. Thus, we propose that the amine−t NCO ligation is a powerful new click reaction for efficient macromolecular coupling.
dc.description.sponsorshipDr Maarten Danial for providing the cyclic peptide.
dc.languageEnglishen
dc.language.isoenen
dc.publisherAmerican Chemical Society
dc.titleA New Methodology for Assessing Macromolecular Click Reactions and Its Application to Amine−Tertiary Isocyanate Coupling for Polymer Ligationen
dc.typeArticle
dc.description.versionThis is the final version of the article. It first appeared from the American Chemical Society via http://dx.doi.org/10.1021/jacs.5b11831en
prism.endingPage4068
prism.publicationDate2016en
prism.publicationNameJournal of the American Chemical Societyen
prism.startingPage4061
prism.volume138en
dc.identifier.doi10.17863/CAM.40
dcterms.dateAccepted2016-02-29en
rioxxterms.funderRoyal Societyen
rioxxterms.identifier.projectWM130055en
rioxxterms.versionofrecord10.1021/jacs.5b11831en
rioxxterms.versionVoRen
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserveden
rioxxterms.licenseref.startdate2016-02-29en
dc.contributor.orcidRoberts, Derrick [0000-0002-4663-7475]
dc.identifier.eissn1520-5126
rioxxterms.typeJournal Article/Reviewen
rioxxterms.funder.project615b7d5f-c0f4-418e-a7c7-64edc898c839en


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record