Antibody catalysis of difficult chemical transformations
Antibody catalysis of difficult chemical transformations
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DOI：
10.1021/ar00032a001
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发表时间：
1993-08
影响因子：
18.3
通讯作者：
P. Schultz;R. Lerner
中科院分区：
文献类型：
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作者：
P. Schultz;R. Lerner
自1986年首次报道抗体催化剂以来，1，2许多化学反应都是由抗体催化的。[3]抗体催化反应的特异性和某些情况下的速率与酶促反应不相上下。在每项研究中，抗体分子的结合能以高度特异性的方式用于控制化学反应的结果。在最早的例子中，选择了具有充分研究的机制的简单变换。例如，抗体用于稳定酯水解中的四面体带负电荷的过渡态。1· 2这些反应之后是更复杂的实验，涉及一般酸、一般碱催化、亲核催化和近似催化。3最近，该领域开始关注通过现有化学方法难以实现的选择性化学转化。这些反应包括“不利的”化学反应、沿着许多几乎相等的反应坐标之沿着的反应、以及反应物的固有反应性或摩尔浓度反转的反应。下面综述与抗体催化这方面有关的最新进展。
Since theoriginal reports of antibody catalysts in1986, 1, 2 many chemical transformations have been catalyzed by antibodies. 3 The specificity and, in some cases, the rates of antibody-catalyzed reactions rival those of enzymatic reactions. In each study, the binding energy of the antibody molecule was used in a highly specific way to control the outcome of a chemical reaction. In the earliest examples, simple transformations with well-studied mechanisms were chosen. For example, antibodies were used to stabilize the tetrahedral, negatively-charged transition state in ester hydrolysis. 1· 2 Thesereactions were followed by more sophisticated experiments involving general acid, gen-eral base catalysis, nucleophilic catalysis, and catalysis by approximation. 3 More recently, the field has begun to focus on selective chemical transformations that are difficult to achieve via existing chemical methods. These include “disfavored” chemical reactions, reactions along one of many nearly equivalent reaction coordinates, and reactions in whichthe inherent reactivity or molarity of the reactants is reversed. Recent advances related to this aspect of antibody catalysis are reviewed below.