CAREER: Reductive Carboxylation of Unsaturated Hydrocarbons

凭借化学部化学催化计划的职业奖，西弗吉尼亚大学（WVU）的Brian Popp教授正在开发在化学合成中利用二氧化碳（CO2）的新催化方法。二氧化碳是一种被低估和利用不足的化学原料。该项目的重点是二氧化碳的反应，以制备用于制造药物，农用化学品和材料的重要化学品。Popp教授的研究使用实验和计算方法来更好地了解这些反应是如何工作的，以及如何改进它们。Popp教授正在开展旨在提高美国科学家的质量和数量的教育活动，特别是来自WVU服务的代表性不足的群体。这是通过加强在课堂和实验室的学术经验来实现的。具体活动旨在提高美国退伍军人在西弗吉尼亚大学有兴趣追求科学，技术，工程和数学（STEM）职业的大学体验。二氧化碳（CO2）是一种有吸引力的可再生资源，用于生产化学品;然而，由于其稳定性，它传统上被化学工业低估。尽管如此，其作为C1原料的更广泛利用可能有助于在未来引导更可持续的碳经济。用CO2催化烯烃还原羧化是一种潜在的强有力的方法，可以产生新的碳-碳键，同时产生最少的废物。Popp教授专注于两种尚未开发的烯烃还原官能化策略：杂（元素）羧化和转移氢金属/羧化。前一种策略采用元素-硼试剂（其中“元素”包括硼、硅和锡）和铜催化剂以使得能够在温和条件下使用CO2进行烯烃双官能化。建立在从铁催化的氢镁化的广泛动力学研究中获得的见解的基础上，后一种策略研究了在单一催化反应中实现氢锌化/羧化的新系统。合理的方法优化是在平行的催化反应机理的研究，使用operando光谱技术，化学计量反应的研究和合理的中间体的制备，以及计算方法的组合完成。为了支持该项目的更广泛的影响，Popp教授正在为西弗吉尼亚大学对STEM感兴趣的美国武装部队退伍军人组织新的培训和职业指导机会，与阿巴拉契亚地区的主要本科院校合作，进行与该项目相关的催化研究，和开发一个新的多媒体工具的有机化学教育。这个奖项反映了NSF的法定使命，并已被认为是值得支持，通过评估使用基金会的学术价值和更广泛的影响评审标准。

With this CAREER Award from the Chemical Catalysis Program in the Chemistry Division, Professor Brian Popp at West Virginia University (WVU) is developing new catalytic methods that utilize carbon dioxide (CO2) in chemical synthesis. CO2 is an undervalued and underutilized chemical raw material. This project is focusing on reactions of CO2 to prepare important chemicals useful for the manufacture of pharmaceuticals, agrochemicals, and materials. Professor Popp's research is using both experimental and computational methods to better understand how these reactions work and how to improve them. Professor Popp is pursuing educational activities aimed at increasing the quality and quantity of U.S. scientists, especially from underrepresented groups served by WVU. This is being accomplished by enhancing the academic experience both in the classroom and the laboratory. Specific activities are aimed at enhancing the university experience for student Veterans of the U.S. Armed Forces at WVU interested in pursuing Science, Technology, Engineering, and Math (STEM) careers.Carbon dioxide (CO2) is an attractive renewable resource for the production of chemicals; however, it is traditionally undervalued by the chemical industry because of its stability. Nevertheless, its broader utilization as a C1 feedstock could help shepherd a more sustainable carbon economy in the future. Catalytic olefin reductive carboxylation with CO2 is a potentially powerful way to create new carbon-carbon bonds while generating minimal waste. Professor Popp is focusing on two underdeveloped olefin reductive functionalization strategies: hetero(element)carboxylation and transfer hydrometallation/carboxylation. The former strategy employs element-boron reagents (where "element" includes boron, silicon, and tin) and copper catalysts to enable olefin difunctionalization using CO2 under mild conditions. Building upon insights gained from extensive kinetic study of iron-catalyzed hydromagnesiation, the latter strategy investigates new systems that achieve hydrozincation/carboxylation in a single catalytic reaction. Rational method optimization is accomplished in parallel with studies of catalytic reaction mechanisms using a combination of operando spectroscopic techniques, studies of stoichiometric reactions and preparation of plausible intermediates, as well as computational methods. In support of the broader impacts of the project, Professor Popp is organizing new training and career mentorship opportunities for STEM-interested student Veterans of the U.S. Armed Forces at WVU, collaborating with a primarily undergraduate institution in the Appalachian region on catalysis research relevant to this project, and developing a new multimedia tool for organic chemistry education.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.