Structure-Reactivity Behavior of Stabilized Carbanions

稳定碳负离子的结构-反应行为

• 批准号: 8921739
• 负责人: Claude Bernasconi
• 金额: $ 35.51万
• 依托单位: University of California-Santa Cruz
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-04-01 至 1994-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8921739&HistoricalAwards=false
• 关键词: Structure; Reactivity; Behavior; Stabilized; Carbanions

In this project in the Organic Dynamics Program of the Chemistry Division, Professor Claude F. Bernasconi in the Chemistry Department of the University of California, Santa Cruz will study the "Kinetics of Proton Transfer and Nucleophilic Additions to Olefins in Solution and in the Gas Phase". There exist characteristic relationships between the structure of the reactants and the rates at which carbon acids are deprotonated to afford carbanions. This study of how resonance and solvation affect reactivity in carbanion-forming reactions will add to our understanding of chemical reactivity (reaction mechanisms) in general. This project will focus on structure-activity relationships, resonance stabilization and solvation of the carbanion, the solvational state of the base (proton transfers) or the nucleophile (addition reactions) which are particularly pertinent to carbanion-forming reactions. The generality of the suggestion that much of the structure-reactivity behavior of carbanion-forming reactions is governed by a lack of synchronization between bond forming processes and other factors such as resonance development, solvation, intramolecular hydrogen bond formation, steric effects, etc., will be scrutinized and quantified.

在化学系有机动力学项目中，加州大学圣克鲁斯分校化学系的克劳德·F·贝纳斯科尼教授将研究“溶液和气相中烯烃的质子转移和亲核加成反应的动力学”。在反应物的结构和碳酸去质子化以获得碳负离子的速率之间存在特征关系。这项关于共振和溶剂化如何影响碳负离子形成反应中的反应性的研究将有助于我们从总体上了解化学反应(反应机理)。本项目将侧重于碳负离子的结构-活性关系、共振稳定和溶剂化、碱的溶剂化状态(质子转移)或亲核试剂(加成反应)，这些都与碳负离子的形成反应特别相关。碳负离子形成反应的大部分结构反应行为是由键形成过程之间缺乏同步控制的这一建议的普遍性，以及其他因素，如共振发展、溶剂化、分子内氢键形成、空间效应等，将被仔细审查和量化。