Mechanisms of Complex Carbocation Rearrangements

在这个由化学系化学结构、动力学机制B项目资助的项目中，加州大学戴维斯分校化学系的Dean J. Tantillo教授将利用现代计算机建模技术，结合实验室实验，揭示控制复杂分子形成机制的化学反应性的基本原理。这项研究将揭示反应性的原则，并测试其普遍性。从这项工作中产生的机理模型将是实用的那些在合成有机，生物，物理有机和化学教育领域的工作。除了通过这项研究发现的化学的根本重要性，所追求的项目将用于培训学生（研究生和本科生，一些来自代表性不足的群体）在多学科方法机械化学，并使他们接触到采用这种技术的职业。此外，为了鼓励盲人和视障学生在STEM领域从事职业，还将开发使盲人和视障学生能够使用应用计算化学的新方法。该研究将通过构建复杂碳阳离子重排的新机械模型来推进机械化学知识。将开发特定的三重态形成碳阳离子重排的具体机制模型，并将从跨越不同类别的碳阳离子的广泛研究中得出具有复杂分子结构的碳阳离子反应性的一般原则。本研究的目标是：（a）使用现代量子化学方法评估各种碳阳离子环化和重排机制导致萜烯天然产物的能量可行性，表征这些过程中涉及的中间体和过渡态结构的电子结构，并评估与这些重排的势能面相关的动力学趋势，（B）评估这些中间体和过渡态结构与酶活性位点中存在的官能团进行非共价/分子间相互作用的能力，并评估这些相互作用的后果，以及（c）揭示复杂系统中碳阳离子反应性的基本一般原理。

In this project funded by the Chemical Structure, Dynamic & Mechanism B Program of the Division of Chemistry, Professor Dean J. Tantillo of the Department of Chemistry at the University of California-Davis will use modern computer modeling techniques, coupled with laboratory experiments, to uncover fundamental principles of chemical reactivity that govern mechanisms of formation of complex molecules. This research will uncover principles of reactivity and test their generality. The mechanistic models resulting from this work will be of utility to those working in the synthetic organic, biological, physical organic and chemical education fields. In addition to the fundamental importance of the chemistry uncovered through this research, the projects pursued will be used to train students (graduate and undergraduate, several from underrepresented groups) in multidisciplinary approaches to mechanistic chemistry and expose them to careers that employ such techniques. In addition, new methods for making applied computational chemistry accessible to blind and visually impaired students will be developed as part of an effort to encourage this group to pursue careers in STEM fields.This research will advance knowledge in mechanistic chemistry through the construction of new mechanistic models for rearrangements of complex carbocations. Specific mechanistic models for particular terpene-forming carbocation rearrangements will be developed, and general principles of reactivity for carbocations with complex molecular architectures will be derived from extensive studies spanning different classes of carbocations. The goals of this research are to (a) use modern quantum chemical methods to assess the energetic viability of various carbocation cyclization and rearrangement mechanisms leading to terpene natural products, characterize the electronic structures of the intermediates and transition state structures involved in these processes, and assess the dynamical tendencies associated with the potential energy surfaces for these rearrangements, (b) assess the ability of these intermediates and transition state structures to engage in noncovalent/intermolecular interactions with functional groups present in enzyme active sites and assess the consequences of these interactions, and (c) uncover fundamental, general principles of carbocation reactivity in complex systems.