Heteroallyl and Alpha-Heterosubstituted Allyllithium Reagents

在有机动力学项目的支持下，杰克曼博士 将研究烯醇化锂的溶液结构。的 将执行以下与此相关的操作 项目：（一）确定混合的 三种烯醇化锂与高氯酸锂的聚集体 和四苯基硼化锂，（ii）动态NMR研究 过程中的混合骨料，（三）溶剂化的研究 一系列取代的苯酚锂，（iv） C-和C-初始速率的综合分析 锂异丁酰苯和锂的O-烷基化 2-异丙基-α-四氢萘酮由甲苯磺酸甲酯在各种 添加有高氯酸锂和锂的溶剂 四苯硼化物，（v）简并质子转移研究 与苯酚锂，和（vi）设计的对映选择性 有机锂试剂 %%% 有机锂化合物提供了合成有机化学家 一些最有效的控制立体声的方法 和区域化学的过程中，涉及新的 碳碳键过去，这一领域的进展 由于缺乏对机械的理解而受到严重阻碍， 这反过来又是缺乏详细知识的结果， 有机锂物种在化学反应中所采用的精确结构 溶液拟议的研究旨在阐明 解决方案结构，然后寻求开发有用的机制， 基于这些结构的概念。特别 溶剂和助溶剂对溶液结构的影响 将研究有机锂物种。此外，新 基于混合聚集体的立体选择性试剂 将探索形成。

With support from the Organic Dynamics Program, Dr. Jackman will study solution structures of lithium enolates. The following sutides will be performed in connection with this project: (i) determination of the structures of the mixed aggregates of three lithium enolates with lithium perchlorate and lithium tetraphenylboride, (ii) NMR studies of dynamic processes in mixed aggregates, (iii) studies of the solvation of a series of substituted lithium phenolates, (iv) comprehen-sive analysis of the initial rates of C- and O-alkylation of lithioisobutyrophenone and lithio 2-isopropyl-alpha-tetralone by methyl tosylate in a variety of solvents with added lithium perchlorate and lithium tetraphenylboride, (v) studies of degenerate proton transfer with lithium phenolates, and (vi) design of enantioselective organolithium reagents. %%% Organolithium compounds provide the synthetic organic chemist with some of the most effective methods for controlling stereo- and regiochemistry in processes that involve formation of new carbon-carbon bonds. In the past, progress in this field has been severely hampered by lack of mechanistic understanding, which in turn is a consequence of lack of detailed knowledge of the precise structures that organolithium species adopt in solution. The proposed studies address the elucidation of solution structures and then seek to develop useful mechanistic concepts that are based upon these structures. The special effects of solvents and cosolvents upon the solution structure of organolithium species will be studied. In addition, new stereoselctive reagents that are based upon mixed aggregate formation will be explored.