Synthetic and Mechanistic Studies of Organometallic Reagents

在化学系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。它们也有助于形成碳-X键，因此是许多其他有机金属试剂(B、锌、钛、铝、铜、Ce、锡、硅、磷、S、硒等)的共同前体，在合成化学中有重要的用途。这项研究的目标是从机理上理解重要的有机金属反应。与任何其他类型的有机金属化合物相比，有机锂试剂的化学性质主要受分子间和分子内与溶剂和碱性侧基的相互作用以及聚集现象的影响。提出的溶剂化和络合的光谱和反应性研究以及产物、选择性和速率的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。在前一次资助期间开发的快速注射核磁共振仪器现已投入使用，将用于检查锂试剂的单个聚集体的反应性和亲电性的单个构象(如酯、硫酸酯和酰胺)的羰基E/Z。有机化学和高分子化学计划支持威斯康星大学麦迪逊分校的汉斯·J·赖克教授，他将提供对合成有机化学程序设计非常重要的一些化学反应和化学物种的机械洞察力。这项资助的工作还将为研究生和本科生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知识。Reich教授已经开发并将继续向科学界提供用于核磁共振模拟(WINDNMR-Pro)和图形和化学结构绘制(WINPLT)的免费计算机程序。该程序生成的图形可以转换为网页或直接用于演示文稿。WINPLT计划约有500名注册用户。他将继续维护一个网站，作为化学社区的参考来源，以帮助预测受酸性影响的所有类型的分子行为。该网站自2001年开通以来，已有超过10万名访问者，目前每周约有1800名访问者。

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.