Mechanisms of Complex Carbocation Rearrangements

凭借此次更新奖，化学结构、动力学和机制项目继续支持Dean J. Tantillo教授的一项建议，该建议使用现代计算化学，结合实验室实验，揭示控制碳正离子重排导致萜烯天然产物的反应性的基本原理。本研究的目标是：(a)使用现代量子化学方法评估导致萜烯天然产物的各种复杂碳正离子环化机制的能量可行性，并表征这些过程中涉及的中间体和过渡态结构的电子结构。(b)评估这些中间体和过渡态结构与酶活性位点的官能团进行非共价/分子间相互作用的能力。简而言之，该项目将揭示与各种复杂重排相关的碳正离子反应性的一般原理。该奖项将促进对不寻常类型化学键的理解，支持博士后、研究生和本科生的培训，并在实验家和计算化学家之间建立一个合作网络。除了通过本研究发现的化学的基本重要性之外，所进行的项目将用于为学生提供机械化学的多学科方法，并使他们接触到利用这些专业知识的职业。这项研究的结果将被纳入加州大学COSMOS暑期项目，面向对科学感兴趣的高中生，以及两年一次的研讨会，为博士后、研究生、本科生和高中生提供理论化学事业的机会。

With this Renewal Award, the Chemical Structure, Dynamics, and Mechanisms Program continues to support Professor Dean J. Tantillo for a proposal that uses modern computational chemistry, coupled with laboratory experiments to uncover the fundamental principles of reactivity that govern mechanisms of carbocation rearrangements leading to terpene natural products. The goals of this research are to (a) use modern quantum chemical methods to assess the energetic viability of various complex carbocation cyclization mechanisms leading to terpene natural products and to characterize the electronic structures of the intermediates and transition state structures involved in these processes. And (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. In short, this project will uncover general principles of carbocation reactivity that are relevant to a wide variety of complex rearrangements. This award will lead to an increased understanding of unusual types of chemical bonding, support the training of postdoctoral, graduate and undergraduate students, and build a network of collaborations between experimentalists and computational chemists. In addition to the fundamental importance of the chemistry uncovered through this research, the projects pursued will be used to provide students with multidisciplinary approaches to mechanistic chemistry and expose them to careers that utilize such expertise. The results of this research will be incorporated into the University of California COSMOS Summer Program for high school students interested in science, and a biennial symposium that exposes postdoctoral, graduate, undergraduate, and high school students to careers in theoretical chemistry.