Synthetic and Mechanistic Studies of Organometallic Reagents

通过这个奖项，有机和大分子化学项目支持威斯康星大学的Hans J. Reich教授，他的研究目标是了解重要的有机金属反应的机制。该研究涉及广泛用于形成碳-碳键的主基团有机金属化合物。它们对形成碳- x键也很有用，因此，它们是其他有机金属试剂（B、Zn、Ti、Al、Cu、Ce、Sn、Si、P、S、Se和Te）的常见前体，在合成化学中具有重要用途。一种新开发的快速注射核磁共振仪器将用于研究有机锂化学的许多方面，目前的知识非常有限：锂试剂的单个聚集体的反应性，羰基化合物的反应性，甚至羰基化合物的单个构象，这些构象过于活跃，无法通过实验室时间尺度实验（醛、酮、酯、酰胺）进行研究。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。通过这个奖项，有机和大分子化学项目支持威斯康星大学的Hans J. Reich教授，他的研究将在合成有机化学领域产生影响，为重要反应物质的行为提供更好的见解。该研究将通过为研究生和本科生提供物理有机化学、有机金属化学、光谱学和有机合成方面的广泛培训，为科学人力做出贡献。为了支持这项研究，已经编写了两个通用的计算机程序，用于核磁共振数据的分析和解释以及化学信息的有效表示，并将继续加强。这些程序已经在网络上免费提供给化学社区。已经建立了若干网址，其中载有与有机和有机金属化学有关的有价值的资料，其形式很容易取得，这些网址将在本项目的过程中继续扩大和加强。

With this award, the Organic and Macromolecular Chemistry Program supports Professor Hans J. Reich of the University of Wisconsin whose research goal is a mechanism understanding of important organometallic reactions. The study involves main group organometallic compounds that are widely used for forming carbon-carbon bonds. They are also useful for forming carbon-X bonds and are, therefore, common precusors to other organometallic reagents (B, Zn, Ti, Al, Cu, Ce, Sn, Si, P, S, Se and Te) with important uses in synthetic chemistry. A newly developed rapid injection NMR apparatus will be used to study a number of aspects of organolithium chemistry for which current knowledge is very limited: the reactivity of individual aggregates of lithium reagents, the reactivity of carbonyl compounds, and even individual conformations of carbonyl compounds too reactive to be studied by laboratory time scale experiments (aldehydes, ketones, esters, amides). 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.With this award, the Organic and Macromolecular Chemistry Program supports Professor Hans J. Reich of the University of Wisconsin whose research will have an impact in the area of synthetic organic chemistry by providing better insight into the behavior of important reactive species. The research will contribute to scientific manpower by providing a broad training in physical organic chemistry, organometallic chemistry, spectroscopy and organic synthesis for graduate and undergraduate students. Two computer programs of general utility for the analysis and interpretation of NMR data and the efficient presentation of chemical information have been written to support this research, and will continue to be enhanced. These programs have been made freely available to the chemical community on the web. Several web sites containing valuable information related to organic and organometallic chemistry in an easily accessible form have been created, and these will continue to be expanded and enhanced in the course of this project.