| DOI | Resolve DOI: https://doi.org/10.1139/cjc-2013-0577 |
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| Author | Search for: Mackenzie, Douglas A.1; Search for: Pezacki, John Paul1 |
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| Affiliation | - National Research Council of Canada. Medical Devices
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| Format | Text, Article |
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| Subject | 1 ,3-dipolar cycloadditions; Bicyclo[6.1.0]nonyne; Click chemistry; Cycloadditions; Nitrones; Strain-promoted alkyne-nitrone cycloaddition (SPANC); Hydrocarbons; Rate constants; Cycloaddition |
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| Abstract | Strain-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. |
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| Publication date | 2014-04 |
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| In | |
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| Language | English |
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| Peer reviewed | Yes |
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| NPARC number | 21275612 |
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| Export citation | Export as RIS |
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| Report a correction | Report a correction (opens in a new tab) |
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| Record identifier | 72f591d7-3ff3-4b27-b08c-19168d011277 |
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| Record created | 2015-07-14 |
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| Record modified | 2020-04-22 |
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