CAREER: Catalytic Activation of Alkenyl C-H Bonds

在化学部化学催化（CAT）计划的支持下，斯克里普斯研究所的Keary Engle正在开发新的催化工艺，以将含有烯烃（含有碳-碳双键（C=C）的分子）的化学原料升级为更复杂的增值分子，用于材料，农业化学和化学生物学/药物化学应用。正在研究能够选择特定烯烃碳-氢键（C-H）键并活化这些键以形成C-X键的钯基催化剂。深入了解这些催化剂如何工作也正在调查，以区分相关的催化转化的关键特征。与此同时，恩格尔博士和他的研究团队正在领导协同活动，以扩大服务不足的学生获得尖端教育经验的机会，并提高科学，技术，工程和数学（STEM）劳动力的多样性和全球竞争力。这些努力包括开发开放获取的研究生课程和学习资源，通过STEM管道联盟扩大提供的编程，该联盟为圣地亚哥当地两年制和四年制大学的不同本科生提供服务，并让来自历史上服务不足的群体的本科生和高中实习生参与研究活动。总的来说，该研究计划有助于提高工业相关化学过程的效率和可持续性，同时支持美国未来的STEM劳动力。将碳-氢键转化为新的碳-碳和碳-杂原子键的催化反应能够快速合成有价值的目标化合物，与传统方法相比，减少了废物的产生。Scripps研究所的Keary Engle和他的团队正在开发钯催化的C（烯基）-H活化反应，并研究促进C（烯基）-H活化的因素与通常从烯烃-钯（II）物种中出现的其他反应歧管。这些催化转化同时被优化，以将容易获得的单取代和二取代的烯烃起始材料转化为更高度取代的烯烃产物，否则难以制备具有限定的区域和立体化学的烯烃产物。活动进一步包括机理研究，指导组调查，并使用烯烃异构化策略，以了解催化过程，并扩大反应性，包括这些催化系统的各种烯烃底物。这个多学科项目将整合机械有机金属化学和有机合成的见解，为高中生，本科生，博士生，博士生和研究生提供全面和创新的培训经验。该奖项反映了NSF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 support from the Chemical Catalysis (CAT) Program in the Division of Chemistry, Keary Engle of the Scripps Research Institute is developing new catalytic processes to upgrade chemical feedstocks containing alkenes (molecules that contain a carbon–carbon double bond (C=C)) to more complex value-added molecules for materials, agrochemical, and chemical biology/medicinal chemistry applications. Palladium-based catalysts that are capable of selecting specific alkene carbon-hydrogen bonds (C-H) bonds and activating these for C-X bond formation are being studied. Insight into how these catalysts work is also being investigated to differentiate key features from related catalytic transformations. In parallel, Dr. Engle and his research team are leading synergistic activities to expand access to cutting-edge educational experiences for underserved students and to enhance the diversity and global competitiveness of the science, technology, engineering, and mathematics (STEM) workforce. These efforts include developing open-access graduate courses and learning resources, expanding programming offered through a STEM pipeline consortium that serves diverse undergraduate students from local two- and four-year colleges in San Diego, and involving undergraduate and high school interns from historically underserved groups in research activities. Overall, this research program is helping to improve the efficiency and sustainability of industrially relevant chemical processes, while bolstering the future STEM workforce of the United States.Catalytic reactions that convert carbon–hydrogen bonds into new carbon–carbon and carbon–heteroatom bonds enable the rapid synthesis of valuable target compounds with reduced waste generation compared to traditional approaches. Keary Engle and his team at the Scripps Research Institute are developing palladium-catalyzed C(alkenyl)–H activation reactions and studying the factors that promote C(alkenyl)–H activation versus other reaction manifolds that typically emerge from alkene–palladium(II) species. These catalytic transformations are simultaneously being optimized to convert readily accessible mono- and disubstituted alkene starting materials into more highly-substituted alkene products that are otherwise difficult to prepare with defined regio- and stereochemistry. Activities further include mechanistic studies, directing group investigations, and the use of alkene isomerization strategies to understand the catalytic process and to broaden the reactivity to include a significant variety of alkene substrates for these catalytic systems. This multidisciplinary project will integrate insights from mechanistic organometallic chemistry, and organic synthesis, providing a holistic and innovative training experience for a diverse group of high school students, undergraduates, Ph.D. students, and postdoctoral fellows.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.