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

在这个由化学部门化学结构、动力学和机制项目资助的项目中，北卡罗来纳州夏洛特大学的Craig A. Ogle和Michael Murphy将使用快速注射（RI）核磁共振波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箱。具体来说，该小组将改进使用有机羧酸盐的烷基化反应，使其更有效，副反应更少。通过对这些反应的理解，该小组试图对试剂和反应条件做出合理的改变，以使他们能够控制对映体选择性。更广泛的影响包括训练本科生和研究生制备和处理气敏试剂、分析仪器的操作和实验设计。这项工作将增强我们对有机酸盐化学中长期寻求的铜（III）中间体的基本理解。有机酸盐与其他有机官能团的反应一直是一个“黑盒子”，与它们的反应性有关。这项研究的重点是将事实与虚构区分开来。这项研究的经济影响可能是重大的，可能会导致制药业的新产品和新方法。

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.