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Chen Y, Tsao K, De Francesco É, et al. Ring Substituent Effects on the Thiol Addition and Hydrolysis Reactions of N-Arylmaleimides. J Org Chem. 2015;80(24):12182-92doi: 10.1021/acs.joc.5b02036.
Chen, Y., Tsao, K., De Francesco, �. �., & Keillor, J. W. (2015). Ring Substituent Effects on the Thiol Addition and Hydrolysis Reactions of N-Arylmaleimides. The Journal of organic chemistry, 80(24), 12182-92. https://doi.org/10.1021/acs.joc.5b02036
Chen, Yingche, et al. "Ring Substituent Effects on the Thiol Addition and Hydrolysis Reactions of N-Arylmaleimides." The Journal of organic chemistry vol. 80,24 (2015): 12182-92. doi: https://doi.org/10.1021/acs.joc.5b02036
Chen Y, Tsao K, De Francesco É, Keillor JW. Ring Substituent Effects on the Thiol Addition and Hydrolysis Reactions of N-Arylmaleimides. J Org Chem. 2015 Dec 18;80(24):12182-92. doi: 10.1021/acs.joc.5b02036. Epub 2015 Dec 03. PMID: 26595216.
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J Org Chem. 2015 Dec 18;80(24):12182-92. doi: 10.1021/acs.joc.5b02036. Epub 2015 Dec 03.

Ring Substituent Effects on the Thiol Addition and Hydrolysis Reactions of N-Arylmaleimides.

The Journal of organic chemistry

Yingche Chen, Kelvin Tsao, Élise De Francesco, Jeffrey W Keillor

Affiliations

  1. Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie-Curie, Ottawa, Ontario K1N 6N5, Canada.

PMID: 26595216 DOI: 10.1021/acs.joc.5b02036

Abstract

Maleimide groups are used extensively in bioconjugation reactions, but limited kinetic information is available regarding their thiol addition and hydrolysis reactions. We prepared a series of fluorogenic coumarin maleimide derivatives that differ by the substituent on their maleimide C═C bond. Fluorescence-based kinetic studies of the reaction with β-mercaptoethanol (BME) yielded the second-order rate constants (k2), while pH-rate studies from pH 7 to 9 gave base-catalyzed hydrolysis rate constants (kOH). Linear free-energy relationships were studied through the correlation of log k2 and log kOH to both electronic (σ(+)) and steric (Es(norm)) parameters of the C═C substituent. These correlations revealed the thiol addition reaction is primarily sensitive to the electronic effects, while steric effects dominate the hydrolysis reaction. These mechanistic studies provide the basis for the design of novel bioconjugation reactants or fluorogenic labeling agents.

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