Controlling the outcome of an N-alkylation reaction by using N-oxide functional groups |
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Authors: | Pearson Russell J Evans Kathryn M Slawin Alexandra M Z Philp Douglas Westwood Nicholas J |
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Affiliation: | Centre for Biomolecular Sciences, School of Chemistry, University of St. Andrews, North Haugh, St. Andrews KY16 9ST, United Kingdom. |
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Abstract: | Covalent modifiers of proteins are of importance in chemical proteomics, an emerging chemical technology used to assign protein function. In this study, high-field (1)H NMR techniques were used to analyze the reaction of the bioactive compound, 2,3-bis(bromomethyl)quinoxaline 1,4-dioxide, with amines (a model system for proteins containing nitrogen-based nucleophiles). Unexpectedly, the results show that a double nucleophilic substitution reaction involving 2 equiv of the amine is preferred to an intramolecular cyclization pathway. A direct comparison with the reaction carried out on a substrate lacking the N-oxide functional groups is also provided. X-ray crystal structures and computational studies are used to rationalize the observed differences in reactivity between the two systems. |
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