AI Article Synopsis
- The study highlights a new approach using nitrile oxides and diazocarbonyls for faster and more versatile metal-free cycloaddition reactions with cyclooctynes, compared to traditional methods with azides.
- Nitrile oxides can be easily generated from oximes using a straightforward oxidation process, enabling a one-pot reaction to insert tags onto carbohydrates.
- The combination of oximes and azides allows for sequential reactions without metals, which simplifies the multifunctionalization of biomolecules and materials without the use of toxic catalysts.
Article Abstract
Although metal-free cycloadditions of cyclooctynes and azides to give stable 1,2,3-triazoles have found wide utility in chemical biology and material sciences, there is an urgent need for faster and more versatile bioorthogonal reactions. We have found that nitrile oxides and diazocarbonyl derivatives undergo facile 1,3-dipolar cycloadditions with cyclooctynes. Cycloadditions with diazocarbonyl derivatives exhibited similar kinetics as compared to azides, whereas the reaction rates of cycloadditions with nitrile oxides were much faster. Nitrile oxides could conveniently be prepared by direct oxidation of the corresponding oximes with BAIB, and these conditions made it possible to perform oxime formation, oxidation, and cycloaddition as a one-pot procedure. The methodology was employed to functionalize the anomeric center of carbohydrates with various tags. Furthermore, oximes and azides provide an orthogonal pair of functional groups for sequential metal-free click reactions, and this feature makes it possible to multifunctionalize biomolecules and materials by a simple synthetic procedure that does not require toxic metal catalysts.
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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3079482 | PMC |
| http://dx.doi.org/10.1021/ja1081519 | DOI Listing |
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