| Abstract
| - Covalent modifiers of proteins are of importance in chemical proteomics, an emerging chemicaltechnology used to assign protein function. In this study, high-field 1H NMR techniques were usedto 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 ispreferred to an intramolecular cyclization pathway. A direct comparison with the reaction carriedout on a substrate lacking the N-oxide functional groups is also provided. X-ray crystal structuresand computational studies are used to rationalize the observed differences in reactivity betweenthe two systems.
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