Kinetics studies of rapid strain-promoted [3+2] cycloadditions of nitrones with bicyclo[6.1.0]nonyne

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DOIResolve DOI: http://doi.org/10.1139/cjc-2013-0577
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TypeArticle
Journal titleCanadian Journal of Chemistry
ISSN0008-4042
Volume92
Issue4
Pages337340; # of pages: 4
Subject1 ,3-dipolar cycloadditions; Bicyclo[6.1.0]nonyne; Click chemistry; Cycloadditions; Nitrones; Strain-promoted alkyne-nitrone cycloaddition (SPANC); Hydrocarbons; Rate constants; Cycloaddition
AbstractStrain-promoted alkyne-nitrone cycloaddition (SPANC) reactions represent a bioorthogonal labeling strategy that is both very rapid and at the same time efficient and selective. Nitrones provide increased reaction rates as well as greater susceptibility toward stereoelectronic modification when compared with organic azides. We find that strain-promoted cycloadditions of cyclic nitrones with bicyclo[6.1.0]nonyne react with second-order rate constants as large as 1.49 L mol-1 s-1 at 25 °C. These reactions display rate constants that are up to 37-fold greater than those of the analogous reactions of benzyl azide with bicyclo[6.1.0]nonyne. We observed that reactions of nitrones with bicyclo[6.1.0]nonyne showed a stronger dependence on substituent effect for the reaction, as evidenced by a larger Hammett Ï value, than that for biaryl-aza-cyclooctanone. We demonstrate the ability to stereoelectronically tune the reactivity of nitrones towards different cyclooctynes in SPANC reactions. This ability to introduce selectivity into different SPANC reactions through substituent provides the opportunity to perform multiple SPANC reactions in one reaction vessel and opens up potential applications in multiplex labeling.
Publication date
PublisherNational Research Council Canada. Research Press
LanguageEnglish
AffiliationNational Research Council Canada; Medical Devices
Peer reviewedYes
NPARC number21275612
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Record identifier72f591d7-3ff3-4b27-b08c-19168d011277
Record created2015-07-14
Record modified2016-10-04
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