New Concepts in Organic Selectivity and Mechanisms

描述(由申请人提供)：传统的理解有机反应中的反应性和选择性的框架不适用于受动态效应影响的反应。有人建议研究动力学效应在化学中一些最常见和最重要的反应中的作用。在氢硼化方面，最初发表的结果对用于解释这些反应中的选择性的所有标准观点提出了质疑；拟议的研究将使用同位素效应和选择性研究来确定动态效应在这些反应中的重要性，并将根据对其作为一种动态现象的理解，探索提高选择性的方法。在[2，3]-Sigmatrotic重排中，初步结果表明，动力学可以为竞争的[2，3]和[1，2]重排提供统一的解释，拟议的机制研究将对这些反应进行广泛的重新解释。在Diels-Alder反应和烯类化合物的[2+2]环加成反应中，最近的研究发现，惯性和质量相关加速的牛顿思想可能是选择性的真正决定因素。拟议的研究将研究如何认识这些影响以及它们对反应的影响范围有多广。在臭氧分解中，初步结果发现，中间的初级臭氧只在分子的一部分中是唯一的“热”的，计划中的研究将检查通过分子的能量运动的结构效应如何影响产物比率。最后，实验结果表明，以前只考虑三原子反应的动态效应，广泛地促进了一般酸碱催化的有机化学和酶化学反应。建议用实验来具体说明该效应在催化中的作用。这项工作与健康有关的原因在于，它影响了人们对重要药物合成中的重要反应和生物途径中的重要反应的理解。 与公共健康相关：药物的合成和生物途径的操纵取决于化学反应的合理设计和控制，而化学反应的合理设计和控制又取决于对化学反应的理解。我们的研究正在提供基本的新闻方法来理解反应，这些反应应该有助于它们的发明、发展和调节。

DESCRIPTION (provided by applicant): The conventional framework for understanding reactivity and selectivity in organic reactions fails for reactions influenced by dynamic effects. It is proposed to investigate the role of dynamic effects in some of the most common and important reactions in chemistry. In hydroboration, initially published results have called into question all of the standard ideas used to explain selectivity in these reaction; the proposed studies would use isotope effects and selectivity studies to determine the breadth of importance of dynamic effects in these reactions, and would explore ways to improve selectivity based on the its understanding as a dynamic phenomenon. In [2,3]-sigmatropic rearrangements, initial results suggest that dynamics can provide a unified explanation for competing [2,3] and [1,2] rearrangements, and the proposed mechanistic studies would a broad reinterpretation of these reactions. In Diels-Alder reactions and the [2 + 2] cycloadditions of ketenes, recent studies have found that the Newtonian ideas of inertia and mass-dependent acceleration can be the real deciding factor in selectivity. The proposed studies would examine ways to recognize these effects and how broadly they affect reactions. In ozonolysis, initial results have found that the intermediate primary ozonide is unique "hot" in only part of the molecule, and the planned studies would examine how structural effects on energy motion through molecules affects product ratios. Finally, experimental results have implicated that a dynamic effect, previously considered only for triatomic reactions, broadly facilitates the general acid-base catalyzed reactions of organic and enzymatic chemistry. Experiments are proposed to define in particular examples the role of the effect in catalysis. 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 biological pathways. PUBLIC HEALTH RELEVANCE: The synthesis of pharmaceuticals and the manipulation of biological pathways depend on the rational design and control of chemical reactions, which in turn depend on the understanding of chemical reactions. Our research is providing fundamental news ways to understand reactions that should aid in their invention, development, and regulation.