一项关于硫酯水解的重原子动力学同位素效应的机理研究。
A mechanistic study of thioester hydrolysis with heavy atom kinetic isotope effects.
作者信息
Marlier John F, Fogle Emily J, Redman Richard L, Stillman Anthony D, Denison Matthew A, Robins Lori I
机构信息
University of Washington-Bothell , Bothell, Washington 98011, United States.
出版信息
J Org Chem. 2015 Feb 6;80(3):1905-8. doi: 10.1021/jo502472m. Epub 2015 Jan 12.
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.
测定了甲酰硫代胆碱水解反应的羰基碳、羰基氧和离去硫的动力学同位素效应（KIEs）。在酸性条件下，(13)k(obs)=1.0312，(18)k(obs)=0.997，(34)k(obs)=0.995；在中性条件下，(13)k(obs)=1.022，(18)k(obs)=1.010，(34)k(obs)=0.996；在碱性条件下，(13)k(obs)=1.0263，(18)k(obs)=0.992，(34)k(obs)=1.000。观察到的动力学同位素效应为过渡态结构中键级的定性描述提供了有用的见解。
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