Structure-Reactivity Behavior of Stabilized Carbanions

在化学学部有机动力学项目中，加州大学圣克鲁斯分校化学系的Claude F. Bernasconi教授将研究“溶液和气相中质子转移和亲核添加烯烃的动力学”。反应物的结构与碳酸去质子生成碳的速率之间存在着特征关系。共振和溶剂化如何影响碳形成反应的反应性的研究将增加我们对化学反应性（反应机制）的总体理解。本项目将重点研究碳离子的构效关系，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），这些与碳离子形成反应特别相关。许多碳形成反应的结构-反应性行为是由键形成过程与其他因素（如共振发展、溶剂化、分子内氢键形成、空间效应等）之间缺乏同步控制的，这一建议的一般性将被仔细审查和量化。

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.