CAREER: Reactive Intermediate Promoted Polycyclization Reactions

职业：反应中间体促进多环化反应

• 批准号: 0449845
• 负责人: Dean Tantillo
• 金额: --
• 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: 2005
• 资助国家: 美国
• 起止时间: 2005-04-01 至 2010-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0449845&HistoricalAwards=false
• 关键词: CAREER; Reactive; Intermediate; Promoted; Polycyclization

With the support of the Organic Dynamics Program in the Chemistry Division, Professor Dean J. Tantillo of the University of California- Davis will perform research that consists of both theoretical and experimental studies of polycyclization mechanisms that are initiated by the generation of an organic reactive intermediate, referred to as Reactive Intermediate Promoted Polycyclization (RIPP) reactions. Polycyclization reactions, single transformations in which molecules with multiple new rings are formed, are among the most efficient chemical transformations known. In many cases, however, the relative importance of geometric, stereoelectronic, electrostatic and hydrophobic effects in controlling the rate, regioselectivity and stereoselectivity of polycyclization is not known. The proposed Modern Quantum Chemistry will be used to elucidate the mechanisms of both synthetic and biosynthetic RIPP reactions in various chemical environments. Particular emphasis will be placed on obtaining a quantitative understanding of catalysis of polycyclization processes using the "theozyme" (theoretical enzyme) method and on the theoretical design of new reactions not previously observed in nature and not previously attempted in the lab, a strategy that Professor Tantillo calls "ab initio reaction design". The overall goal of the proposed research is to provide a detailed set of guidelines for designing efficient polycyclization processes. The Organic and Macromolecular Chemistry Program supports Professor Dean J. Tantillo of the University of California- Davis whose projects described in this proposal are designed so that students can construct complete stories that involve the development of theoretical models to explain experimental observations, application of these models to the design of new reactions, and testing of these designs through laboratory experiments. The results of these studies will be presented at an annual conference that will be organized during the grant period by the PI and his students, which will bring together theoretical and computational chemists from graduate and undergraduate educational institutions and from the pharmaceutical and software development industries.

在化学系有机动力学项目的支持下，加州大学戴维斯分校的 Dean J. Tantillo 教授将开展由有机反应中间体的生成引发的多环化机制的理论和实验研究。 ，称为反应性中间体促进多环化（RIPP）反应。多环化反应是形成具有多个新环的分子的单一转化，是已知的最有效的化学转化之一。 然而，在许多情况下，几何、立体电子、静电和疏水效应在控制多环化的速率、区域选择性和立体选择性方面的相对重要性尚不清楚。拟议的现代量子化学将用于阐明各种化学环境中合成和生物合成 RIPP 反应的机制。将特别强调使用“theozyme”（理论酶）方法对多环化过程的催化进行定量理解，以及以前在自然界中未观察到且以前未在实验室中尝试过的新反应的理论设计，这是教授的策略Tantillo 称之为“从头开始反应设计”。拟议研究的总体目标是为设计有效的多环化过程提供一套详细的指南。 有机和高分子化学项目支持加州大学戴维斯分校 Dean J. Tantillo 教授，他在本提案中描述的项目旨在帮助学生构建完整的故事，其中涉及开发理论模型来解释实验观察结果以及这些模型的应用设计新反应，并通过实验室实验测试这些设计。这些研究的结果将在 PI 及其学生在资助期间组织的年度会议上公布，会议将汇集来自研究生和本科生教育机构以及制药和软件开发行业的理论和计算化学家。