New Concepts In Organic Selectivity and Mechanisms

项目总结/摘要 理解有机化合物反应性和选择性的传统框架 对于受动态效应影响的反应，反应失败。建议调查 一些最常见和最重要的化学反应中的动力学效应。我们 最近，在σ迁移重排中的动态效应的工作导致了成功的 控制这些反应选择性的策略。我们计划将这一战略扩展到 一系列广泛的反应，并开发催化对映选择性σ-迁移 重新安排我们研究的另一个新重点是溶剂动力学在 反应.在Wittig反应和芳烃硝化反应的基础上， 了解溶剂动力学如何影响一系列实验观察 极性反应。烷氧基自由基裂解反应给了我们一个难得的机会，在一个接近不同的 连续的障碍，结构和过剩的能量，以检查规则，支配的发病和 动态效应的程度。烷氧基自由基对化学的广泛领域很重要，我们 旨在了解动力学如何影响他们的反应。在我们之前的工作中， 硼氢化和臭氧分解，我们的目的是检查反应引起的产生 在普通反应中的极“热”中间体或产物。这与健康的关系 工作源于它对控制反应选择性的策略和 了解重要的反应，在重要的药用物质的合成， 在生物学途径中起重要作用的反应。

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.