Synthetic and Mechanistic Studies of Organometallic Reagents

9320696 Reich这项研究的重点是从机理上了解有机锂化学中的一些重要反应和过程。由于有机锂试剂的化学性质可能比任何其他类型的有机金属化合物更多地由分子间和分子内与溶剂和侧基的相互作用所主导，溶剂化、络合和立体化学的光谱和反应性研究以及产物、选择性和速率研究将有助于更好地理解这些现象。由于实验将在合成化学家使用的条件和溶剂中进行，因此这些研究将使有机锂试剂的化学反应具有更好的可预测性，并扩大其应用范围。具体项目包括配位助溶剂(主要是HMPA)和离子对结构对反应性的作用、螯合效应、烯基/丙叉基锂试剂、立体化学定义的有机锂试剂的制备和异构化机理，以及锂的类金属交换反应。有了这个奖项，合成有机计划支持威斯康星大学麦迪逊分校化学系的汉斯·J·赖克博士的研究。赖克教授将把他的工作重点放在从机理上理解有机锂化学中的一些重要反应和过程。由于其中许多试剂在有机合成中起着核心作用，特别是对于非常重要的碳-碳键形成反应，这些研究将使有机锂试剂的化学反应具有更好的可预测性，并扩大其应用范围。***

9320696 Reich The focus of this research is to gain a mechanistic understanding of a number of important reactions and processes in organolithium chemistry. Because the chemical properties of organolithium reagents, perhaps more than any other class of organometallic compound, are dominated by inter- and intramolecular interactions with solvents and pendant groups, the spectroscopic and reactivity studies of solvation, chelation and stereochemistry together with product, selectivity and rate studies will give a better understanding of these phenomena. Since the experiments will be carried out under the conditions and in solvents in which they are used by synthetic chemists, the studies will allow better predictability of the chemical reactions of organolithium reagents and the expansion of the applications of them. Specific projects include coordinating cosolvents (principally HMPA) and the role of ion pair structure on reactivity, chelation effects, allenyl/propargyllithium reagents, preparation and mechanism of epimerization of stereochemically defined organolithium reagents, and the lithium metalloid exchange reaction. %%% With this award the Synthetic Organic Program is supporting the research of Dr. Hans J. Reich of the Department of Chemistry at the University of Wisconsin, Madison. Professor Reich will focus his work on gaining a mechanistic understanding of a number of important reactions and processes in organolithium chemistry. Since many of these reagents play a central role in organic synthesis, especially for the very important carbon-carbon bond forming reactions, these studies will allow better predictability of the chemical reactions of organolithium reagents and an expansion of their applications. ***