AB Initio Calculations on Eliminations and Proton Transfers

在有机动力学项目的支持下，威廉·H· 小桑德斯，化学系的教授， 罗切斯特正在进行量子化学计算消除 和质子转移反应。 氟取代的计算 碳负离子允许评估负离子的作用 超共轭和消除反应的研究 氟代烃解决了E1cb和E2反应之间的边界 途径。 控制取向和立体化学的因素 协同消除反应是通过考虑 电荷分布、同位素效应和离子配对。 特别 注意力放在发展对顺反的理解上 二分法，其中顺式烯烃通过反消除产生，而反式烯烃通过反消除产生， 烯烃是通过顺式消除产生的。 表面上最简单的化学反应包括 一个带正电荷的氢原子（质子）从 分子中的一个位置到另一个位置。 尽管表面上很简单， 然而，这些反应的实验结果表明， 复杂性 通过计算技术的应用， 在有机动力学项目的支持下，William H. 小桑德斯，化学系的教授， 罗切斯特正在探索质子转移的基本方面 反应. 他的研究还延伸到反应分析 引发的质子损失，特别是集中在是否 这些反应的总反应路径包括同时 消除一个额外的组或如果这种消除发生 在最初的质子损失之后。 这些问题是 各种各样的化学反应，教授 桑德斯的研究使我们对 控制它们的因素。

With the support of the Organic Dynamics Program, Professor William H. Saunders, Jr., of the Department of Chemistry at the University of Rochester, is carrying out quantum chemical calculations on elimination and proton transfer reactions. Calculations on fluorine-substituted carbanions permit the assessment of the role of negative ion hyperconjugation, and studies of elimination reactions of fluorohydrocarbons address the borderline between E1cb and E2 reaction pathways. Factors governing the orientation and stereochemistry of concerted elimination reactions are examined through consideration of charge distributions, isotope effects, and ion pairing. Particular attention is placed on developing an understanding of the syn-anti dichotomy, wherein cis olefins are produced by anti elimination but trans olefins are produced by syn elimination. Among the superficially simplest chemical reactions are those involving the transfer of a single positively-charged hydrogen atom (a proton) from one place in a molecule to another. Despite the apparent simplicity of such reactions, however, experimental results indicate appreciable complexity. Through the application of calculational techniques and with the support of the Organic Dynamics Program, Professor William H. Saunders, Jr., of the Department of Chemistry at the University of Rochester, is exploring the fundamental aspects of proton transfer reactions. His studies also extend to the analysis of reactions initiated by the loss of a proton, focusing in particular on whether the overall reaction path for such reactions involves simultaneous elimination of an additional group or if such elimination occurs subsequently to the initial proton loss. These issues are central to an extraordinarily wide variety of chemical reactions, and Professor Saunders' studies are leading to a fundamental understanding of the factors controlling them.