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涉及阴离子模板在过渡态的大环化反应的动力学分析。

Kinetic analysis for macrocyclizations involving anionic template at the transition state.

作者信息

Martí-Centelles Vicente, Burguete M Isabel, Luis Santiago V

机构信息

Departamento de Química Inorgánica y Orgánica, Universitat Jaume I, E12071 Castellón de la Plana, Spain.

出版信息

ScientificWorldJournal. 2012;2012:748251. doi: 10.1100/2012/748251. Epub 2012 Apr 22.

DOI:10.1100/2012/748251
PMID:22666148
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC3347868/
Abstract

Several kinetic models for the macrocyclization of a C₂ pseudopeptide with a dihalide through a S(N)2 reaction have been developed. These models not only focus on the kinetic analysis of the main macrocyclization reaction, but also consider the competitive oligomerization/polymerization processes yielding undesired oligomeric/polymeric byproducts. The effect of anions has also been included in the kinetic models, as they can act as catalytic templates in the transition state reducing and stabilizing the transition state. The corresponding differential equation systems for each kinetic model can be solved numerically. Through a comprehensive analysis of these results, it is possible to obtain a better understanding of the different parameters that are involved in the macrocyclization reaction mechanism and to develop strategies for the optimization of the desired processes.

摘要

已经开发了几种用于C₂拟肽与二卤化物通过S(N)2反应进行大环化的动力学模型。这些模型不仅关注主要大环化反应的动力学分析，还考虑了产生不需要的低聚物/聚合物副产物的竞争性低聚/聚合过程。动力学模型中还包括了阴离子的影响，因为它们可以在过渡态中充当催化模板，降低并稳定过渡态。每个动力学模型的相应微分方程组都可以通过数值方法求解。通过对这些结果的全面分析，可以更好地理解大环化反应机制中涉及的不同参数，并制定优化所需过程的策略。

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