Kinetic and computational evidence for an intermediate in the hydrolysis of sulfonate esters

被引：15
|
作者：
Babtie, Ann C. [2 ]
Lima, Marcelo F. [1 ,2 ]
Kirby, Anthony J. [1 ]
Hollfelder, Florian [2 ]
机构：
[1] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England
[2] Univ Cambridge, Dept Biochem, Cambridge CB2 1GA, England
来源：
ORGANIC & BIOMOLECULAR CHEMISTRY | 2012年 / 10卷 / 40期
基金：
英国工程与自然科学研究理事会; 英国生物技术与生命科学研究理事会;
关键词：
ALKALINE-PHOSPHATASE SUPERFAMILY; P-NITROPHENYL PHOSPHATE; SINGLE TRANSITION-STATE; CATALYTIC PROMISCUITY; SULFATE ESTERS; REACTIVITY; MECHANISM; NUCLEOPHILES; INHIBITION; METABOLISM;
D O I：
10.1039/c2ob25699a
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The hydrolytic reactions of sulfonate esters have previously been considered to occur by concerted mechanisms. We now report the observation of a break in a Bronsted correlation for the alkaline hydrolysis of aryl benzenesulfonates. On either side of a break-point, beta(leaving) group values of -0.27 (pK(a) < 8.5) and -0.97 (pK(a) > 8.5) are measured. These data are consistent with a two-step mechanism involving a pentavalent intermediate that is also supported by QM/MM calculations. The emerging scenario can be explained by the combined effect of a strong nucleophile with a poor leaving group that compel a usually concerted reaction to favour a stepwise process.
引用
收藏
页码：8095 / 8101
页数：7
相关论文
共 50 条
  • [1] The Alkaline Hydrolysis of Sulfonate Esters: Challenges in Interpreting Experimental and Theoretical Data
    Duarte, Fernanda
    Geng, Ting
    Marloie, Gael
    Al Hussain, Adel O.
    Williams, Nicholas H.
    Kamerlin, Shina Caroline Lynn
    JOURNAL OF ORGANIC CHEMISTRY, 2014, 79 (07): : 2816 - 2828
  • [2] Experimental and Computational Evidence for a Loose Transition State in Phosphoroimidazolide Hydrolysis
    Li, Li
    Lelyveld, Victor S.
    Prywes, Noam
    Szostak, Jack W.
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (12) : 3986 - 3989
  • [3] The influence of polyphenols on the hydrolysis and formation of volatile esters in wines during aging: An insight of kinetic equilibrium reaction
    Ling, Mengqi
    Cui, Dongsheng
    Zhu, Baoqing
    Li, Demei
    Mu, Haibin
    Li, Jin
    Shi, Ying
    Duan, Changqing
    Lan, Yibin
    FOOD CHEMISTRY, 2025, 464
  • [4] Hydrolysis of phosphate esters in aqueous solution promoted by cobalt(III)-tetraamine metallohydrolases: Chromatographic and spectroscopic studies
    Bhengu, Thokoza
    Wood, Tim
    Shumane, Manelisi
    Tafesse, Fikru
    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS, 2019, 194 (1-2) : 87 - 101
  • [5] Density Functional Theory and ab Initio Computational Evidence for Nitrosamine Photoperoxides: Hammett Substituent Effects in the Photogeneration of the Nitrooxide Intermediate
    Greer, Edyta M.
    Kwon, Kitae
    PHOTOCHEMISTRY AND PHOTOBIOLOGY, 2018, 94 (05) : 975 - 984
  • [6] A simple method for the alkaline hydrolysis of esters
    Theodorou, Vassiliki
    Skobridis, Konstantinos
    Tzakos, Andreas G.
    Ragoussis, Valentine
    TETRAHEDRON LETTERS, 2007, 48 (46) : 8230 - 8233
  • [7] Hydrolysis of esters in subcritical and supercritical water
    Krammer, P
    Vogel, H
    JOURNAL OF SUPERCRITICAL FLUIDS, 2000, 16 (03): : 189 - 206
  • [8] Micellar effects on aromatic esters hydrolysis
    Brandariz, I.
    Iglesias, E.
    COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS, 2014, 454 : 180 - 188
  • [9] Computational study on the hydrolysis of halomethanes
    Ruan, Min
    Hou, Hua
    Wang, Baoshan
    Li, Wen
    Chen, Yue
    Deng, Xiangyi
    Zuo, Xiaohua
    THEORETICAL CHEMISTRY ACCOUNTS, 2018, 137 (12)
  • [10] Computational study on the hydrolysis of halomethanes
    Min Ruan
    Hua Hou
    Baoshan Wang
    Wen Li
    Yue Chen
    Xiangyi Deng
    Xiaohua Zuo
    Theoretical Chemistry Accounts, 2018, 137
12345