title: A mechanistic study of thioester hydrolysis with heavy atom kinetic isotope effects.
abstract: 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.
authors.affiliation: University of Washington-Bothell , Bothell, Washington 98011, United States.
authors.forename: John F
authors.initials: JF
authors.lastname: Marlier
authors.forename: Emily J
authors.initials: EJ
authors.lastname: Fogle
authors.forename: Richard L
authors.initials: RL
authors.lastname: Redman
authors.forename: Anthony D
authors.initials: AD
authors.lastname: Stillman
authors.forename: Matthew A
authors.initials: MA
authors.lastname: Denison
authors.forename: Lori I
authors.initials: LI
authors.lastname: Robins
mesh_terms: D006868:Hydrolysis; D007554:Isotopes / Q000737:chemistry*; D007700:Kinetics; D015394:Molecular Structure; D013457:Sulfur Compounds / Q000737:chemistry*; D013860:Thiocholine / Q000031:analogs & derivatives / Q000737:chemistry*
chemical_list: D007554:Isotopes; D013457:Sulfur Compounds; D013860:Thiocholine