New Concepts In Organic Selectivity and Mechanisms

项目摘要/摘要 理解有机化合物的反应性和选择性的传统框架 对于受动态效果影响的反应，反应失败。建议对这一角色进行调查 化学中一些最常见和最重要的反应中的动态效应。我们的 在Sigmatrotic重排中使用动态效应的工作最近导致了一个成功的 控制这些反应中的选择性的策略。我们计划将这一战略扩展到 一系列广泛的反应和开发催化对映体选择性的Sigmatrotic 重新安排。我们研究的另一个新的重点是溶剂动力学在 反应。根据Wittig反应和芳烃硝化的最新结果，我们将 了解溶剂动力学如何影响一系列实验观察 极地反应。烷氧基裂解反应给了我们一个难得的机会来改变近乎 连续体势垒、结构和过剩能量，以检查支配起始点和 动态效果的程度。烷氧基对化学的广泛领域都很重要，我们 目的了解动态如何影响他们的反应。在我们之前的工作基础上 硼氢化和臭氧分解，我们的目标是研究由产生 在普通反应中非常“热”的中间体或产物。它与健康的关联性 工作源于它对控制反应选择性的两种策略和 了解在合成具有重要药用价值的物质和 在生物途径中很重要的反应。

Project Summary / Abstract 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. Our work with dynamic effects in sigmatropic rearrangements has recently led to a successful strategy for the control of selectivity in these reactions. We plan to extend this strategy to cover a broad array of reactions and develop catalytically enantioselective sigmatropic rearrangements. Another new emphasis in our research is the role of solvent dynamics in reactions. Following up on recent results with the Wittig reaction and arene nitration, we will develop an understanding of how solvent dynamics affects experimental observations in a series of polar reactions. Alkoxy radical cleavage reactions give us a rare opportunity to vary on a near continuum barriers, structure, and excess energy to examine the rules that govern the onset and degree of dynamic effects. Alkoxy radicals are important to broad areas of chemistry, and we aim to understand how dynamics affects their reactions. Following on our prior work with hydroboration and ozonolysis, we aim to examine the reactions induced by the generation of extremely “hot” intermediates or products in ordinary reactions. The health-relatedness of this work derives from its impact on both strategies to control reaction selectivity and the understanding of reactions important in the synthesis of medicinally important substances and reactions important in biological pathways.