CAREER: Reductive Carboxylation of Unsaturated Hydrocarbons

职业：不饱和烃的还原羧化

• 批准号: 1752986
• 负责人: Brian Popp
• 金额: $ 67.5万
• 依托单位: West Virginia University Research Corporation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-03-01 至 2025-02-28
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1752986&HistoricalAwards=false
• 关键词: CAREER; Reductive; Carboxylation; Unsaturated; Hydrocarbons

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.

西弗吉尼亚大学 (WVU) 的 Brian Popp 教授凭借化学系化学催化项目颁发的职业奖，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且未充分利用的化学原料。该项目的重点是二氧化碳反应，以制备可用于制造药品、农用化学品和材料的重要化学品。波普教授的研究正在使用实验和计算方法来更好地了解这些反应如何发挥作用以及如何改进它们。波普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，特别是来自西弗吉尼亚大学服务的代表性不足群体的科学家。这是通过增强课堂和实验室的学术经验来实现的。具体活动旨在增强西弗吉尼亚大学美国武装部队退伍军人学生的大学体验，他们有兴趣从事科学、技术、工程和数学 (STEM) 职业。二氧化碳 (CO2) 是一种用于生产化学品的有吸引力的可再生资源;然而，由于其稳定性，化学工业传统上低估了它的价值。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。用二氧化碳催化烯烃还原羧化是一种潜在的强大方法，可以在产生最少废物的同时产生新的碳-碳键。 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）羧化和转移加氢金属化/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，在温和条件下使用二氧化碳实现烯烃双官能化。基于对铁催化水镁化的广泛动力学研究获得的见解，后一种策略研究了在单一催化反应中实现氢化/羧化的新系统。合理的方法优化是与催化反应机制的研究并行完成的，使用操作光谱技术、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。为了支持该项目的更广泛影响，波普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学生组织新的培训和职业指导机会，并与阿巴拉契亚地区的一所主要本科院校合作开展与此相关的催化研究该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Synthesis and Reactivity of Ampy-Based Ruthenium(II) Catalysts for Transfer Hydrogenation of Ketones

Ampy 基钌(II) 酮转移加氢催化剂的合成及反应活性

• DOI: 10.1021/acs.organomet.1c00444
• 发表时间: 2022-04
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Amason, Edith K.;Rajabimoghadam, Khashayar;Baughman, Notashia N.;Ghareeb, C. Roland;Bourgeois, Samantha K.;Keuk, Channita;Manacsa, Gayle;Popp, Brian V.;Garcia;Ferrence, Gregory M.;et al
• 通讯作者: et al

Synthesis of a Borylated Ibuprofen Derivative through Suzuki Cross-Coupling and Alkene Boracarboxylation Reactions

通过 Suzuki 交叉偶联和烯烃硼羧化反应合成硼化布洛芬衍生物

• DOI: 10.3791/64571
• 发表时间: 2022-01
• 期刊: Journal of Visualized Experiments
• 作者: Knowlden, Steven W.;Abeysinghe, Randika T.;Swistok, Amanda D.;Ravenscroft, Alexis C.;Popp, Brian V.
• 通讯作者: Popp, Brian V.

Experimental and Computational Analysis of CO 2 Addition Reactions Relevant to Copper-Catalyzed Boracarboxylation of Vinyl Arenes: Evidence for a Phosphine-Promoted Mechanism

与铜催化乙烯基芳烃硼羧化相关的 CO 2 加成反应的实验和计算分析：膦促进机制的证据

• DOI: 10.1021/acs.organomet.0c00488
• 发表时间: 2021-01
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Baughman, Notashia N.;Akhmedov, Novruz G.;Petersen, Jeffrey L.;Popp, Brian V.
• 通讯作者: Popp, Brian V.

Beneficial Effect of a Secondary Ligand on the Catalytic Difunctionalization of Vinyl Arenes with Boron and CO 2

辅助配体对硼和 CO 2 乙烯基芳烃催化双官能化的有益作用

• DOI: 10.1002/cctc.201901197
• 发表时间: 2019-08
• 期刊: ChemCatChem
• 影响因子: 4.5
• 作者: Perrone, Trina M.;Gregory, Amy S.;Knowlden, Steven W.;Ziemer, Natalie R.;Alsulami, Rabah N.;Petersen, Jeffrey L.;Popp, Brian V.
• 通讯作者: Popp, Brian V.

Benzannulation and Hydrocarboxylation Methods for the Synthesis of a Neopentylene-Fused Analogue of Ibuprofen

合成布洛芬新戊烯稠合类似物的苯并环化和加氢羧化方法

• DOI: 10.1021/acsomega.1c04943
• 发表时间: 2021-11-09
• 期刊: ACS Omega
• 影响因子: 4.1
• 作者: Martin AC;Rogers JA;Batsomboon P;Morrison AE;Ramsubhag RR;Popp BV;Dudley GB
• 通讯作者: Dudley GB