Entropic factors provide unusual reactivity and selectivity in epoxide-opening reactions promoted by water.

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

SUBMITTER: Byers JA 

PROVIDER: S-EPMC3801047 | biostudies-literature | 2013 Oct

REPOSITORIES: biostudies-literature