Hydrolysis Reactions of p-Nitrophenyl Trifluoroacetate and S-Ethyl Trifluorothioacetate

被引:0
|
作者
Suggs, Jack B. [1 ]
Melko, Joshua J. [1 ]
机构
[1] Univ North Florida, Dept Chem & Biochem, Jacksonville, FL 32224 USA
来源
MOLECULES | 2025年 / 30卷 / 02期
关键词
water structures; kinetic rates; esters; thioesters; potential energy surface; cleavage reactions; hydrogen bonding effects; general solvation effects; WATER-CATALYZED HYDROLYSIS; TRANSITION-STATE STRUCTURE; MP2; ENERGY; BASIS-SETS; REARRANGEMENTS; METABOLISM; DYNAMICS; ATOMS;
D O I
10.3390/molecules30020268
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
The formation of water structures can provide significant benefits in organic reactions, stabilizing charge and lowering activation energies. Hydrolysis reactions will frequently rely on water networks to accomplish these goals. Here, we used computational chemistry and experimental kinetics to investigate a model thioester molecule S-ethyl trifluorothioacetate, and extended work on a previously characterized ester p-nitrophenyl trifluoroacetate. We found that the rate-determining steps in these reactions are heavily influenced by the nature of the leaving group. The hydrolysis of S-ethyl trifluorothioacetate was much slower than p-nitrophenyl trifluoroacetate for this reason. We explored differences in the reaction orders with respect to water and examined details of calculated potential energy surfaces of these hydrolysis reactions, highlighting the roles of solvation effects and transition state structures.
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页数:9
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