Collaborative Research: Enantioselectivity in Heterogeneous Catalysts via the Addition of Chiral Modifiers

合作研究：通过添加手性修饰剂实现多相催化剂的对映选择性

基本信息

批准号：
1855199
负责人：
Wilfred Tysoe
金额：
$ 26.8万
依托单位：
University of Wisconsin-Milwaukee
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2019
资助国家：
美国
起止时间：
2019-05-01 至 2022-04-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1855199&HistoricalAwards=false
关键词：
Collaborative Research Enantioselectivity Heterogeneous Catalysts

项目摘要

Biomolecular building blocks can exhibit either right- or left-handed symmetries; such building blocks are known as enantiomers. All biomolecules found in living organisms have only one "handedness', that is, the molecules exist only in one enantiomeric form. Moreover, different enantiomers of the same molecule can interact with living organisms in completely different ways, sometimes beneficially and sometimes with catastrophic effects. As the wrong handedness can cause harm, pharmaceuticals and agrochemicals must be synthesized in enantiopure forms. This synthesis may be accomplished by purification after the drug has been synthesized, but that approach is often difficult and cumbersome. It is preferable to develop processes in which only one enantiomer of the drug is made. Enantiopure syntheses can be accomplished by using solid-phase catalysts with surfaces that are specifically modified to preferentially produce molecules with only one handedness. There have been a number of trial-and-error efforts to discover such heterogeneous catalysts, but success has so far been limited. Drs. Tysoe (University of Wisconsin-Milwaukee) and Zaera (University of California-Riverside) have considerable experience in studying the surface chemistry of catalytic systems under ideal conditions. Their research project focuses on understanding the molecular interactions that control enantio-selectivity in more complex and realistic systems for the advanced manufacturing of pharmaceuticals. Drs. Tysoe and Zaera are strongly committed to educating women and minorities, in particular, Hispanic students both in the laboratory and through formal courses. They participate in outreach programs at Milwaukee and Riverside, and are incorporating the research associated with this project into those activities. With funding from the Chemical Catalysis Program of the Chemistry Division, Drs. Tysoe and Zaera are studying the surface chemistry of model palladium(111) and platinum(111) chiral catalysts modified by a cinchonidine analog, 1-(1-naphthyl) ethylamine (NEA), using scanning tunneling microscopy (STM), infrared absorption spectroscopy, reactivity measurements, and first-principles density functional theory (DFT) calculations. This research provides a molecular-level understanding of the diastereomeric interactions between a number of prochiral reactants and NEA, and the forces that control them. They are investigating whether the detailed molecular understanding of the chiral surface chemistry from single-crystal studies in ultrahigh vacuum is relevant to the reaction pathways occurring under realistic conditions, that is, under atmospheric pressures and in the presence of a liquid phase. The resulting understanding may provide insights into how to improve catalytic selectivity. The research may facilitate the targeted design of supported heterogeneous enantioselective catalysts. Such an ability is expected to have a significant economic impact in the pharmaceutical and agrochemical industries. Drs. Tysoe and Zaera focus on educating women and minorities through their research and outreach programs as part of the broader impacts of the project.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.

生物分子的构件可以表现出右手或左手的对称性；这样的构件被称为对映异构体。在生物体中发现的所有生物分子都只有一种“交接性”，也就是说，分子仅以一种对映体形式存在。此外，同一分子的不同对映异构体可以完全不同的方式与生物有机体相互作用，有时有时会在有时，有时会在灾难性的范围内造成危害，有时会造成危害。这种合成可以通过纯化后的纯化来完成，但是这种方法通常很困难且繁琐。迄今为止，这种催化剂的催化剂是有限的。 Tysoe和Zaera强烈致力于对妇女和少数群体进行教育，他们在实验室和正式课程中都参加了Milwaukee和Riverside。铂（111）使用扫描的隧道显微镜（STM），通过神经氨酸类似物（1-（1-萘基）乙胺（NEA）修饰的手性催化剂，红外吸收光谱，反应性测量值和第一promention intivions Inifortion formention neverition nevention nevention nevention note note note note note note note note noteRELIEN a MOLECERIENS。他们的反应物和NEA，以及它们的控制力。异类的对照式催化剂。审查标准。