New Concepts in Organic Selectivity and Mechanisms

描述（由申请人提供）：用于理解有机反应中的反应性和选择性的常规框架对于受动态效应影响的反应失效。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。在硼氢化反应中，最初发表的结果对用于解释这些反应中选择性的所有标准思想提出了质疑;拟议的研究将使用同位素效应和选择性研究来确定这些反应中动态效应的重要性，并将探索基于其作为动态现象的理解来提高选择性的方法。在[2，3]-σ迁移重排反应中，动力学可以为[2，3]和[1，2]的竞争重排提供统一的解释，而所提出的机理研究将对这些反应进行更广泛的重新解释。在Diels-Alder反应和烯酮的[2 + 2]环加成反应中，最近的研究发现，牛顿的惯性和质量相关的加速度是决定选择性的真实的因素。拟议中的研究将探讨如何认识这些影响，以及它们对反应的影响有多广泛。在臭氧分解中，初步结果发现，中间初级臭氧化物仅在分子的一部分中是独特的"热"，计划中的研究将研究结构对分子能量运动的影响如何影响产物比例。最后，实验结果表明，以前只考虑三原子反应的动态效应，广泛地促进了有机和酶化学的一般酸碱催化反应。实验中提出定义在特定的例子中的作用的效果在催化。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，这些反应在合成医学上重要的物质和生物学途径中重要的反应中很重要。

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.