Enolate Aggregation and Reactivity

有机化学和高分子化学项目继续支持加州大学伯克利分校化学系Andrew Streitwieser博士的工作。这项研究旨在扩展早期关于烯醇酸锂聚合及其与含有活化双键的有机卤化物、磺酸盐和羰基化合物反应的平衡和动力学方面的工作。有待探索的变量包括空间效应、共轭作用、可与锂离子配位的附加官能团、溶剂效应以及添加剂如HMPA和胺的影响。研究涉及对空气敏感的稀释液，将在一个独特的手套箱设施中进行，通过石英光纤电缆将恒温样品架连接到外部计算机控制的UV/Vis光谱仪。实验将得到理论计算的补充。预计这项工作将带来更多的理解，这将有助于合成化学家设计出更好的方法来形成包含新的碳-碳键的有机分子。

With this renewal award the Organic and Macromolecular Chemistry Program is continuing its support for the work of Dr. Andrew Streitwieser of the Department of Chemistry of the University of California at Berkeley. The research aims to extend earlier work on the equilibria and kinetics involved in the aggregation of lithium enolates and their reactions with organic halides, sulfonates, and carbonyl compounds containing activated double bonds. Variables to be explored include steric effects, conjugation, added functionality which can coordinate with the lithium ions, solvent effects, and the effects of additives such as HMPA and amines. Research, which involves dilute air-sensitive solutions, will be done in a unique glove box facility, with a thermostated sample holder connected by quartz fiber-optic cables to an external computer-controlled uv/vis spectrometer. Experiments will be complemented by theoretical computations. The increased understanding expected to result from this work will aid synthetic chemists to devise improved ways to form organic molecules containing new carbon-carbon bonds.