Synthetic and Mechanistic Studies of Organometallic Reagents

在化学学部有机动力学项目的支持下，威斯康星大学麦迪逊分校的Hans J. Reich教授将继续对几个涉及主要族有机金属化合物的项目进行基础研究。有机锂试剂被广泛用于形成碳-碳键。它们对形成碳- x键也很有用，因此是许多其他有机金属试剂（B、Zn、Ti、Al、Cu、Ce、Sn、Si、P、S、Se等）的常见前体，在合成化学中具有重要用途。这项研究的目标是对重要的有机金属反应的机理理解。与其他任何一类有机金属化合物相比，有机锂试剂的化学性质主要受与溶剂和碱性悬垂基团的分子间和分子内相互作用以及聚集现象的影响。提出的溶剂化和螯合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，更好地预测有机锂试剂的化学反应，并扩大锂试剂的应用范围。在之前的拨款期间开发的快速注射核磁共振仪现在已经开始工作，将用于检查锂试剂的单个聚集体的反应性和亲电试剂的单个构象（羰基E/Z），如酯、硫酯和酰胺。有机和大分子化学项目支持威斯康星大学麦迪逊分校的Hans J. Reich教授，他将提供对合成有机化学过程设计非常重要的一些化学反应和化学物种的机理见解。这项资助的工作还将为研究生和本科生的研究人员提供物理有机化学、有机金属化学、光谱学和有机合成方面的广泛背景。Reich教授已经开发并将继续为科学界提供用于核磁共振模拟（WINDNMR-Pro）和图形和化学结构图绘制（WINPLT）的免费计算机程序。该程序生成的图纸可以转换成网页或直接用于演示文稿。WINPLT程序大约有500个注册用户。他将继续维护一个网站，作为化学社区的参考来源，以帮助预测受酸度影响的所有类型的分子行为。自2001年开通以来，该网站的访问量已超过10万，目前每周的访问量约为1800人。

With the support of the Organic Dynamics Program in the Chemistry Division, Professors Hans J. Reich at the University of Wisconsin-Madison will continue fundamental studies on several projects involving main group organometallic compounds. Organolithium reagents are widely used for forming carbon-carbon bonds. They are also useful for forming carbon-X bonds, and thus are common precursors to many other organometallic reagents (B, Zn, Ti, Al, Cu, Ce, Sn, Si, P, S, Se to name a few) with important uses in synthetic chemistry. The goal of the research is a mechanistic understanding of important organometallic reactions. More than perhaps any other class of organometallic compound, the chemical properties of organolithium reagents are dominated by inter - and intramolecular interactions with solvents and basic pendant groups, as well as by aggregation phenomena. The proposed spectroscopic and reactivity studies of solvation and chelation together with product, selectivity and rate studies will result in a better understanding of these phenomena, better predictability of the chemical reactions of organolithium reagents, and expansion of the applications of lithium reagents. A rapid injection NMR apparatus developed during the previous grant period is now functional and will be used to examine the reactivity of individual aggregates of lithium reagents and the individual conformations (carbonyl E/Z) of electrophiles such as esters, thioesters, and amides.The Organic and Macromolecular Chemistry Program supports Professors Hans J. Reich at the University of Wisconsin-Madison who will provide mechanistic insight into some chemical reactions and chemical species of great importance to the design of procedures in synthetic organic chemistry. The work supported by this grant will also provide a broad background in physical organic chemistry, organometallic chemistry, spectroscopy, and organic synthesis to graduate and undergraduate researchers. Professor Reich has developed and will continue to provide to the scientific community free computer programs useful for NMR simulations (WINDNMR-Pro) and for graphics and chemical structure drawing (WINPLT). The program produces drawings that can be converted into web pages or used directly in presentations. There are about 500 registered users of the WINPLT program. He will continue to maintain a website that is a reference source for the chemical community to aid in predictions of all types of molecular behavior that are affected by acidity. The website has had over 100,000 visitors since its opening in 2001, and currently has about 1800 visitors a week.