Designer Silver Catalysts for Selective Bond Amidations

用于选择性键酰胺化的设计银催化剂

基本信息

批准号：
1954325
负责人：
Jennifer Schomaker
金额：
$ 49万
依托单位：
University of Wisconsin-Madison
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2020
资助国家：
美国
起止时间：
2020-06-01 至 2024-05-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1954325&HistoricalAwards=false
关键词：
Designer Silver Catalysts Selective Bond

项目摘要

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.

通过此奖项，NSF化学部的化学催化计划支持威斯康星大学麦迪逊大学化学系的詹妮弗·席玛克（Jennifer Schomaker）教授的研究，以设计新的催化剂，这些催化剂将原料化学物质转化为有用的构建基础，以构成药品和农业化学物质的合成。正在开发的银催化剂将称为烷烃和烷烃的有机分子的共同部分变成称为胺的含氮基团。重要的是，这些催化剂也被调整为选择特定类型的烷烃或烷烃，以在包含多个烷烃和/或烷烃键的分子中进行胺化过程。 Schomaker教授及其多元化的毕业生和本科研究人员正在研究有关这些催化剂如何工作的问题，以学习如何提高其高级化学物质和材料制造的性能。这项研究的一部分也被改编成大学教学实验室实验，以便在早期阶段吸引学生参与研究经验。该项目的绿色方面正在教学实验室课程活动中，为本科生提供指导的询问机会。低成本的模块化催化剂的开发用于将C-H键转换为C-N键的可调节转换是一个长期以来的挑战，这对于实现药物和材料应用中重要的分子碎片的流线合成至关重要。为了解决这个问题，Schomaker教授及其研究小组正在设计银催化剂，可以通过金属催化的硝基转移过程来控制C-H键向C-N键的选择性转换。这些研究结合了机械，光谱和计算研究，以了解银色催化剂的不同结构元素如何影响与底物的相互作用，并促进特定的C-H键的选择性反应性。还探索了案例研究，以说明这些新合成工具对制备映射胺的影响，制造药品的合成构建块以及新型氨基糖的设计。最终，这项工作正在为新的银色催化剂建立一般设计原则，这些催化剂可以覆盖先天反应性的偏好，并且不需要指挥小组进行C-H胺胺。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子优点和更广泛影响的审查标准来通过评估来获得支持的。

项目成果

期刊论文数量（8）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Silver-catalyzed enantioselective functionalizations of alkenes and alkynes: A short review

DOI：
10.1016/j.cogsc.2021.100483
发表时间：
2021-03
期刊：
Green and Sustainable Chemistry
影响因子：
0
作者：
Mahzad Dehghany;J. Schomaker
通讯作者：
Mahzad Dehghany;J. Schomaker

Taming Nitrene Reactivity with Silver Catalysts

用银催化剂控制氮烯反应性

DOI：
10.1055/s-0040-1707197
发表时间：
2020
期刊：
Synlett
影响因子：
2
作者：
Vine, Logan E.;Zerull, Emily E.;Schomaker, Jennifer M.
通讯作者：
Schomaker, Jennifer M.

Chemo- and enantioselective intramolecular silver-catalyzed aziridinations of carbamimidates

银催化的氨基甲酸酯的化学和对映选择性分子内氮丙啶化

DOI：
10.1039/d3cc05670h
发表时间：
2023
期刊：
Chemical Communications
影响因子：
4.9
作者：
Trinh, Tuan Anh;Fu, Yue;Hu, Derek B.;Zappia, Soren A.;Guzei, Ilia A.;Liu, Peng;Schomaker, Jennifer M.
通讯作者：
Schomaker, Jennifer M.

Tunable Silver-Catalyzed Nitrene Transfer: From Chemoselectivity to Enantioselective C–H Amination

可调银催化氮烯转移：从化学选择性到对映选择性 C–H 胺化