Organic Reactions and Interactions in Solution

溶液中的有机反应和相互作用

• 批准号: 9528027
• 负责人: William Jorgensen
• 金额: $ 48.82万
• 依托单位: Yale University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1996
• 资助国家: 美国
• 起止时间: 1996-01-01 至 1998-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9528027&HistoricalAwards=false
• 关键词: Organic; Reactions; Interactions; Solution

William Jorgensen is supported by a grant from the Theoretical and Computational Chemistry Program to continue his research involving theoretical simulations of organic reaction mechanisms in solution. This work involves the use of ab initio MO theory to obtain information regarding the gas phase potential energy surface for organic reactions. This information is then used in conjunction with Monte Carlo simulation techniques to simulate the chemical reaction in solution. The combination of these methodologies provides estimates of the solvated free energy changes involved in a chemical reaction, and provides important background information on the role which solvation plays in chemical reactions. These methodologies are being applied to various important reaction mechanisms including the (2+2) cycloaddition, oxy-Cope rearrangements, and alkoxide alkylations. Simulations of host-guest systems are also being performed with an emphasis on predicting binding preferences of importance in the design of catenanes and rotaxanes which show promise as the basis for molecular devices. Computer-assisted design of catalytic hosts using transition state geometries and charges obtained from ab initio calculations is also being pursued. This research is important for the elucidation of molecular-level effects of solvation on reaction rates, intermolecular interactions and host-guest binding in solution, and the influence of solvation on the structures of molecules. The theoretical studies closely parallel and complement experimental work on the optimization of organic reactions and on the development of catalysts, selective receptors for organic molecules including drugs and metabolites, materials with novel properties, and molecular devices.

威廉·乔根森得到了理论和 计算化学计划继续他的研究， 溶液中有机反应机理的理论模拟。 这 工作涉及使用从头计算MO理论来获得信息 关于有机反应的气相势能面。 然后将此信息与蒙特卡罗模拟结合使用 模拟溶液中化学反应的技术。 的 这些方法的组合提供了溶剂化的 化学反应中的自由能变化， 重要的背景资料的作用，溶剂化发挥 化学反应。 这些方法正在应用于各种 重要的反应机理，包括（2+2）环加成，氧-Cope 重排和醇盐烷基化。 主客体模拟 系统也正在执行，重点是预测结合 在索烃和轮烷的设计中， 有望成为分子器件的基础。 计算机辅助 使用过渡态几何形状和电荷设计催化主体 从从头计算得到的结果也在进行之中。 这项研究对于阐明分子水平的效应具有重要意义 溶剂化对反应速率、分子间相互作用和 溶液中的主客体结合，以及溶剂化对 分子的结构。 理论研究密切平行， 补充优化有机反应的实验工作， 催化剂的发展，有机物的选择性受体 分子，包括药物和代谢物，具有新的 性质和分子器件。