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A new methodology for assessing macromolecular click reactions and its application to amine–tertiary isocyanate coupling for polymer ligation

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Gody, Guillaume, Roberts, Derrick A., Maschmeyer, Thomas and Perrier, Sébastien (2016) A new methodology for assessing macromolecular click reactions and its application to amine–tertiary isocyanate coupling for polymer ligation. Journal of the American Chemical Society, 138 (12). pp. 4061-4068. doi:10.1021/jacs.5b11831 ISSN 0002-7863.

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Official URL: http://dx.doi.org/10.1021/jacs.5b11831

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Abstract

Click 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-tNCO). Using our bifunctional linker coupling strategy, we show that the amine–tNCO 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–tNCO 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–tNCO ligation is a powerful new click reaction for efficient macromolecular coupling.

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Science, Engineering and Medicine > Science > Chemistry
Library of Congress Subject Headings (LCSH): Polymers -- Experiments -- Research, Isocyanates, Amines
Journal or Publication Title: Journal of the American Chemical Society
Publisher: American Chemical Society
ISSN: 0002-7863
Official Date: 29 February 2016
Dates:
DateEvent
29 February 2016Published
January 2016Accepted
11 November 2015Submitted
Volume: 138
Number: 12
Page Range: pp. 4061-4068
DOI: 10.1021/jacs.5b11831
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Open Access (Creative Commons)
Date of first compliant deposit: 24 May 2016
Date of first compliant Open Access: 25 May 2016
Funder: Gates Cambridge Trust, Royal Society (Great Britain). Wolfson Research Merit Award (RSWRMA), Australian Research Council (ARC), Licella (Firm)
Grant number: WM130055 (RSWRMA), P100200339 (ARC)

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