Pd-Catalyzed Allylic Oxidation Reactions

利用氧（一种绿色氧化剂）氧化有机化学品以制造特定的目标化学品，仍然是化学工业面临的重大挑战。威斯康星大学麦迪逊分校的香农·斯塔尔博士正在开发一种催化剂，使氧在简单原料化学物质选择性转化为药物的过程中可以用作氧化剂。C-H键的氧化是制药工业特别感兴趣的，因为它使药物分子能够有效地制备或修饰以优化其性质。有机分子有大量不同的碳氢键，斯塔尔博士开发的反应被设计成只氧化这些分子中特定的碳氢键。这种选择性是通过催化剂设计，结合与默克研究实验室的科学家合作的新颖实验技术来实现的。这种校企合作旨在增强研究的广泛影响。参加默克现场研究访问的学生正在与斯塔尔博士和威斯康星大学麦迪逊分校的校园安全代表合作，帮助在大学研究环境中实施新的基于行业的安全协议。人力资源开发工作的目标是通过利用威斯康星大学麦迪逊分校现有的多个项目，增强研究生群体的多样性。在化学部化学催化项目的资助下，威斯康星大学麦迪逊分校的香农·斯塔尔博士正在开发新的烯丙基C-H氧化反应，这种反应与使用O2作为化学计量氧化剂兼容。由于Pd催化剂的新辅助配体的发现、设计和开发，靶向反应以前所未有的催化剂控制的化学选择性、区域选择性和立体选择性进行。催化剂和反应开发工作与严格的机制研究密切相关，这些机制研究实施了创新的机制工具，如能够在线连续输送压力下的O2的高压核磁共振反应器和operando x射线吸收光谱。与默克研究实验室的科学家进行战略合作，提供高通量实验和分析，以发现催化烯丙基氧化反应，从而实现天然产品或现有药物的选择性后期功能化。参加默克公司现场研究访问的学生正在与斯塔尔博士和威斯康星大学麦迪逊分校的校园安全代表合作，帮助实施他们在默克公司期间遇到的新的安全协议。此外，这些学生正在与Stahl博士合作开发一个反应筛选和优化统计分析模块，用于威斯康星大学麦迪逊分校的研究生课程。

The oxidation of organic chemicals to make specific target chemicals using oxygen, a green oxidant, remains a significant challenge for the chemical industry. Dr. Shannon Stahl of the University of Wisconsin-Madison is developing catalysts that enable oxygen to be used as an oxidant in selective conversions of simple feedstock chemicals into pharmaceuticals. The oxidation of C-H bonds is of particular interest to the pharmaceutical industry because it enables drug molecules to be prepared efficiently or modified to optimize their properties. Organic molecules have a large number of different C-H bonds, and the reactions being developed by Dr. Stahl are designed to oxidize only specific C-H bonds in those molecules. This selectivity is accomplished by catalyst design, combined with novel experimental techniques in collaboration with scientists at Merck Research Laboratories. This university-industry collaboration is leveraged to enhance the broader impact of the research. Students participating in on-site research visits at Merck are working with Dr. Stahl and campus safety representatives at UW-Madison to help implement new industry-based safety protocols within the University research environment. Human resource development efforts target enhanced diversity in the graduate student population by leveraging multiple programs in place at UW-Madison.With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Shannon Stahl of the University of Wisconsin at Madison is developing new allylic C-H oxidation reactions that are compatible with the use of O2 as the stoichiometric oxidant. The targeted reactions proceed with unprecedented catalyst-controlled chemo-, regio- and stereoselectivity, enabled by the discovery, design and development of new ancillary ligands for the Pd catalyst. The catalyst and reaction development efforts are closely coupled to rigorous mechanistic studies that implement innovative mechanistic tools such as a high-pressure NMR reactor capable of on-line continuous delivery of O2 at pressure and operando X-ray absorption spectroscopy. A strategic collaboration with scientists at Merck Research Laboratories provides access to high-throughput experimentation and analysis to discover catalytic allylic oxidation reactions that enable selective late-stage functionalization of natural products or existing pharmaceuticals. Students participating in on-site research visits at Merck are working with Dr. Stahl and campus safety representatives at UW-Madison to help implement new safety protocols they encounter during their time at Merck. In addition, these students are working with Dr. Stahl to develop a reaction screening and optimization statistical analysis module for implementation in the graduate curriculum at UW-Madison.