Mechanisms of Complex Carbocation Rearrangements

复杂碳正离子重排机制

• 批准号: 0957416
• 负责人: Dean Tantillo
• 金额: $ 37.5万
• 依托单位: University of California-Davis
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2010
• 资助国家: 美国
• 起止时间: 2010-09-01 至 2013-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0957416&HistoricalAwards=false
• 关键词: Mechanisms; Complex; Carbocation; Rearrangements

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.

通过此续签奖励，化学结构，动力学和机制计划继续支持Dean J. Tantillo教授使用现代计算化学的提案，再加上实验室实验，以揭示控制碳定位重排机制的基本反应性原理。这项研究的目标是（a）使用现代量子化学方法来评估导致萜烯天然产物的各种复杂碳环化环化机制的能量可行性，并表征中间体和过渡状态结构的电子结构。 （b），评估这些中间体和过渡状态结构的能力，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。简而言之，该项目将发现与各种复杂重排相关的碳分配反应性的一般原则。该奖项将导致人们对异常类型的化学键合，支持博士后，研究生和本科生的培训，并在实验者和计算化学家之间建立合作网络。除了通过这项研究发现的化学反应的基本重要性外，所追求的项目还将用于为学生提供多学科的机械化学方法，并将其暴露于利用这种专业知识的职业。这项研究的结果将纳入加利福尼亚大学宇宙大学夏季计划，适用于对科学感兴趣的高中学生，并进行了两年一次的研讨会，该计划将使博士后，毕业生，本科生和高中生暴露于理论化学的职业。