A Mechanistic Study of Thioester Hydrolysis with Heavy Atom Kinetic Isotope Effects

作者:Marlier John F; Fogle Emily J; Redman Richard L; Stillman Anthony D; Denison Matthew A; Robins Lori I*
来源:Journal of Organic Chemistry, 2015, 80(3): 1905-1908.
DOI:10.1021/jo502472m

摘要

The carbonyl-C, carbonyl-O, and leaving-S kinetic isotope effects (KIEs) were determined for the hydrolysis of formylthiocholine. Under acidic conditions, (13)k(obs) = 1.0312, (18)k(obs) = 0.997, and (34)k(obs) = 0.995; for neutral conditions, (13)k(obs) = 1.022, (18)k(obs) = 1.010, and (34)k(obs) = 0.996; and for alkaline conditions, (13)k(obs) = 1.0263, (18)k(obs) = 0.992, and (34)k(obs) = 1.000. The observed KIEs provided helpful insights into a qualitative description of the bond orders in the transition state structure.

  • 出版日期2015-2-6

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