Entropic factors provide unusual reactivity and selectivity in epoxide-opening reactions promoted by water
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Byers-2013-Entropic factors pro.pdf
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1.17 MB
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Author(s)
Byers, Jeffery A.
Jamison, Timothy F.
Date Issued
September 2013
Journal
Proceedings of the National Academy of Sciences
Publisher
National Academy of Sciences (U.S.)
Citation
Byers, J. A., and T. F. Jamison. “Entropic Factors Provide Unusual Reactivity and Selectivity in Epoxide-Opening Reactions Promoted by Water.” Proceedings of the National Academy of Sciences 110, no. 42 (October 15, 2013): 16724–16729.
Version
Final published version
Abstract
Despite the myriad of selective enzymatic reactions that occur in water, chemists have rarely capitalized on the unique properties of this medium to govern selectivity in reactions. Here we report detailed mechanistic investigations of a water-promoted reaction that displays high selectivity for what is generally a disfavored product. A combination of structural and kinetic data indicates not only that synergy between substrate and water suppresses undesired pathways but also that water promotes the desired pathway by stabilizing charge in the transition state, facilitating proton transfer, doubly activating the substrate for reaction, and perhaps most remarkably, reorganizing the substrate into a reactive conformation that leads to the observed product. This approach serves as an outline for a general strategy of exploiting solvent-solute interactions to achieve unusual reactivity in chemical reactions. These findings may also have implications in the biosynthesis of the ladder polyether natural products, such as the brevetoxins and ciguatoxins.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
https://doi.org/10.1073/pnas.1311133110
