Journal of the American Chemical Society
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The large, normal 18(V/K) reported here for 17X-PTDH catalysis
is similar to observations for phosphate triester hydrolyses,21,47
which proceed via tight TSs. Supplementing the data with
computation provides a TS structure that is consistent with the
observed H/D and 18O KIEs. This structure illustrates a tighter TS
than would be expected for the hydrolysis of phosphate mono- and
diesters and provides the first insights into the TS for the unusual
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ASSOCIATED CONTENT
Supporting Information
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The Supporting Information is available free of charge on the ACS
Publications website.
Full citation for reference 33; experimental procedures; 18(V/K)
data sets; Cartesian coordinates and thermodynamics of computed
structures; computational methodology; discussions on
commitment factors, binding isotope effects and hydride tunneling.
AUTHOR INFORMATION
Corresponding Authors
*Phone: (217) 244-5360. Fax: (217) 244-8068. E-mail:
*E-mail: gwhowe@illinois.edu
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENTS
We thank X. Guan and L. Zhu for assistance with NMR data
acquisition, and D. Herschlag for helpful discussions. Data were
collected on a 600 MHz NMR funded by NIH S10-RR028833.
GWH is the recipient of an NSERC Postdoctoral Fellowship. This
work was supported by the Howard Hughes Medical Institute.
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