Designer Silver Catalysts for Selective Bond Amidations

美国国家科学基金会化学部的化学催化项目通过该奖项支持威斯康星大学麦迪逊分校化学系的Jennifer Schomaker教授设计新的催化剂，将原料化学品转化为合成药物和农用化学品的有用组成部分。正在开发的银催化剂将被称为烯烃和烷烃的有机分子的共同部分转化为含氮基团被称为胺。重要的是，这些催化剂也被调整为选择特定类型的烯烃或烷烃，在含有多个烷烃和/或烯烃键的分子中进行胺化过程。Schomaker教授和她的研究生和本科生研究团队正在研究这些催化剂是如何工作的问题，以了解如何提高它们的性能，用于先进的化学品和材料制造。本研究的部分内容也被改编为本科教学实验室实验，以吸引学生在研究经验的早期阶段。这个项目的绿色方面正在进行教学实验课程活动，为本科生提供指导探究的机会。开发低成本的模块化催化剂，用于将C-H键可调转化为C-N键，这是一个长期存在的挑战，对于实现制药和材料应用中重要分子片段的流线型合成至关重要。为了解决这个问题，Schomaker教授和她的研究小组正在设计银催化剂，可以通过金属催化的亚硝基转移过程控制C-H键到C-N键的选择性转化。这些研究结合了机理、光谱和计算研究，以了解银催化剂的不同结构元素如何影响与底物的相互作用，并促进与特定C-H键的选择性反应活性。案例研究也在探索中，以说明这些新的合成工具对制备对映体富集胺、构建药物合成构件和设计新型氨基糖的影响。最终，这项工作将建立新的银催化剂的一般设计原则，这些催化剂可以超越固有的反应性偏好，并且不需要C-H酰胺化的指导基团。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

With this award, the Chemical Catalysis Program of the NSF Division of Chemistry is supporting the research of Professor Jennifer Schomaker of the Department of Chemistry at the University of Wisconsin Madison to design new catalysts that convert feedstock chemicals into useful building blocks for the synthesis of pharmaceuticals and agrochemicals. The silver catalysts that are being developed change common parts of organic molecules called alkenes and alkanes into nitrogen-containing groups called amines. Importantly, these catalysts are also being tuned to select a specific type of alkene or alkane to undergo the amination process within a molecule containing multiple examples of alkane and/or alkene bonds. Professor Schomaker and her diverse team of graduate and undergraduate researchers are examining questions about how these catalysts work in order to learn how to improve their performance for the advanced manufacturing of chemicals and materials. Portions of this study are also being adapted for undergraduate teaching laboratory experiments to engage students at an early stage in research experiences. Green aspects of this project are being pursued in teaching laboratory course activities that provide guided inquiry opportunities for undergraduates.The development of low-cost, modular catalysts for the tunable conversion of C-H bonds to C-N bonds is a long-standing challenge that is crucial for achieving streamlined syntheses of important molecular fragments in pharmaceutical and material applications. To address this issue, Professor Schomaker and her research group are designing silver catalysts that can control the selective transformation of C-H bonds to C-N bonds through metal-catalyzed nitrene transfer processes. These investigations combine mechanistic, spectroscopic, and computational studies to understand how the different structural elements of the silver catalysts influence interactions with substrates and promote selective reactivity with specific C-H bonds. Case studies are also being explored to illustrate the impact of these new synthetic tools for the preparation of enantioenriched amines, the construction of synthetic building blocks for pharmaceuticals, and the design of novel amino sugars. Ultimately, this work is establishing general design principles for new silver catalysts that can override innate reactivity preferences and do not require a directing group for C-H amidation.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.