New Concepts in Organic Selectivity and Mechanisms

通过对不同反应的机理研究，提出了探索传统的理解有机反应的框架是不够的领域。在文献中的工作临界质量，无论是从我们的小组和其他人，是支持一个大大扩展的重要性，在化学中的普通有机反应在溶液中的动态效应。当反应涉及具有两个相邻鞍点的势能面时，反应的产物由与形成可能产物的任何势垒无关的动力学效应决定。建议检查各种可能涉及动态效应的重要反应，以了解并最终控制其选择性。它还建议使用机械的研究，使反应的选择性，特别是熵的选择性的影响，高度准确的预测产品的比例是可能的水平的理解。最后，提出了一些重要的新反应的理解和控制的选择性的目的，机制的研究。这项工作的健康相关性来自于它对理解重要的反应的影响，这些反应在医学重要物质的合成中很重要，在生物合成途径中也很重要。

Through mechanistic studies of diverse reactions, it is proposed to explore areas in which the conventional framework for understanding organic reactions is not adequate. A critical mass of work in the literature, both from our group and others, is supporting a greatly expanded importance for dynamic effects in the chemistry of ordinary organic reactions in solution. When a reaction involves a potential energy surface having two adjacent saddle points, the product of the reaction is decided by dynamic effects that are unrelated to any barrier for formation of the possible products. It is proposed to examine a variety of important reactions that are likely to involve dynamic effects in order to understand and ultimately control their selectivity. It is also proposed to use mechanistic studies to bring the understanding of reaction selectivity, particularly entropic effects on selectivity, to the level where highly accurate predictions of product ratios are possible. Finally, mechanistic studies are proposed with the aim of understanding and controlling selectivity in some important new reactions. The health-relatedness of this work derives from its impact on the understanding of reactions important in the synthesis of medicinally important substances and reactions important in biosynthetic pathways.