Rapid Injection NMR Studies of Copper(I) and Copper(III) Organocuprates

在这个由化学系化学结构、动力学和机制计划资助的项目中，北卡罗来纳大学夏洛特分校的克雷格·A·奥格尔和迈克尔·墨菲将使用快速注入(RI)核磁共振光谱技术研究有机铜试剂。这种方法将进一步扩展导致碳-碳键形成的合成反应的工具包。具体地说，该小组将使用有机铜酸盐改进烷基化反应，使其更高效，副反应更少。通过发展对这些反应的理解，该小组寻求对试剂和反应条件进行合理的改变，以使它们能够控制对映体的选择性。更广泛的影响包括培训本科生和研究生在空气敏感试剂的准备和操作、分析仪器的操作和实验设计方面的培训。这项工作将加深我们对有机铜化学中备受追捧的铜(III)中间体的基本认识。有机铜酸盐与其他有机官能团的反应一直是一个“黑匣子”，有许多与它们的反应性相关的知识；这项研究的重点是将事实与虚构分开。这项研究的经济影响可能是巨大的，可能会导致制药业出现新的产品和方法。

In this project funded by the Chemical Structure, Dynamics and Mechanisms Program of the Chemistry Division, Craig A. Ogle and Michael Murphy of the University of North Carolina at Charlotte will study organocopper reagents using rapid injection (RI) NMR spectroscopy. This approach will further expand the toolkit of synthetic reactions leading to carbon-carbon bond formations. Specifically, the group will improve alkylation reactions using organocuprates so that they are more efficient with fewer side reactions. By developing an understanding of these reactions, the group seeks to make rational changes to the reagents and reaction conditions to allow them to control enantioselectivity. The broader impacts involve training undergraduate and graduate students in the preparation and handling of air-sensitive reagents, the operation of analytical instrumentation, and experimental design. This work will enhance our fundamental understanding about long sought after copper(III) intermediates in organocuprate chemistry. Reactions of organocuprates with other organic functional groups have been a "black box" with much lore associated with their reactivity; This research is focused on separating fact from fiction. The economic impact of this research could be significant, potentially leading to new products and methodologies in the pharmaceutical industry.