Cooperative Enamine-Hard Metal Lewis Acid Catalysis for New Asymmetric Organic Transformations

烯胺-硬金属路易斯酸协同催化新的不对称有机转化

• 批准号: 1954422
• 负责人: Hong Wang
• 金额: $ 49万
• 依托单位: University of North Texas
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1954422&HistoricalAwards=false
• 关键词: Cooperative; Enamine; Hard; Metal; Lewis

With this award, the Chemical Catalysis Program is funding Dr. Hong Wang of the University of North Texas to develop new catalytic methods to synthesize chiral molecules. Chiral molecules exist as non-superimposable mirror images, the same difference as left and right hands. Many molecules, especially naturally-occurring organic compounds and many pharmaceuticals, are chiral and the two mirror image forms of the molecule often have different biological properties. Therefore, an important challenge in modern organic synthesis is to control the handedness of the product. The reactions being developed in this project are designed to provide concise and versatile synthetic pathways to construct 5- and 7-membered ring systems, with control of handedness, a difficult feat with currently available synthetic methods. Dr. Wang is actively engaged in joint efforts to attract a diverse group of students to science, technology, engineering, and mathematics (STEM) fields. Her outreach activities build upon her research and includes outreach summer research programs for undergraduate students from minority schools and high school students to establish interest in STEM fields at an early stage. Dr. Hong Wang and her research team are developing novel catalytic systems through merging enamine catalysis with hard metal Lewis acid catalysis. The feasibility of the reversed soft-hard strategy is investigated to solve the critical acid-base quenching problem involved in cooperative acid-base catalysis. Also, under investigation is which factors affect the formation of enamine from primary arylamines and ketones. [3+2] and [4+3] reactions are developed using cooperative enamine-hard metal Lewis acid catalysis to construct 5- and 7-membered ring systems. In addition, a new class of bimetallic complexes is explored to serve as chiral hard metal Lewis acid catalysts in asymmetric catalysis. The density functional theory (DFT) calculations are carried out to understand the structure-activity of these bimetallic catalysts and the mechanisms of the [3+2] and [4+3] reactions. To address the broader impacts of this project, Dr. Wang is actively engaged in initiating outreach programs to provide summer research opportunities to undergraduate and high school students with a focus on attracting female and minority students into STEM fields.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.

通过这一奖项，化学催化计划资助北得克萨斯大学的王宏博士开发合成手性分子的新催化方法。手性分子以不可重叠的镜像形式存在，与左手和右手的区别相同。许多分子，特别是自然生成的有机化合物和许多药物，都是手性的，分子的两种镜像形式往往具有不同的生物学特性。因此，控制产物的左旋性是现代有机合成中的一个重要挑战。该项目中正在开发的反应旨在提供简洁和多功能的合成途径来构建五元环和七元环系统，并控制左旋手，这是目前可用的合成方法难以实现的壮举。王博士积极参与联合努力，吸引不同群体的学生进入科学、技术、工程和数学(STEM)领域。她的外展活动建立在她的研究基础上，包括为少数族裔学校的本科生和高中生提供的外展暑期研究计划，以在早期阶段建立对STEM领域的兴趣。王宏博士和她的研究团队正在通过将烯胺催化与硬金属Lewis酸催化相结合来开发新的催化系统。研究了反向软硬策略用于解决协同酸碱催化中的关键酸碱猝灭问题的可行性。此外，还在调查哪些因素影响伯芳胺和酮形成烯胺。[3+2]和[4+3]反应是利用协作烯-胺-硬金属Lewis酸催化构建的五元环和七元环体系。此外，还探索了一类新的双金属络合物作为手性硬金属Lewis酸催化剂用于不对称催化。用密度泛函理论(DFT)计算了这些双金属催化剂的结构-活性以及[3+2]和[4+3]反应的机理。为了应对这一项目的更广泛影响，王博士积极参与启动外展计划，为本科生和高中生提供暑期研究机会，重点是吸引女性和少数族裔学生进入STEM领域。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势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

Asymmetric Synthesis of Chromans Through Bifunctional Enamine‐Metal Lewis Acid Catalysis

双功能烯胺-金属路易斯酸催化不对称合成色满

• DOI: 10.1002/chem.202200224
• 发表时间: 2022
• 期刊: Chemistry – A European Journal
• 作者: Davis, Jacqkis;Gharaee, Mojgan;Karunaratne, Chamini V.;Cortes Vazquez, Jose;Haynes, Mikayla;Luo, Weiwei;Nesterov, Vladimir N.;Cundari, Thomas;Wang, Hong
• 通讯作者: Wang, Hong

Can Primary Arylamines Form Enamine? Evidence, α-Enaminone, and [3+3] Cycloaddition Reaction

• DOI: 10.1021/acs.joc.1c01462
• 发表时间: 2021-10-05
• 期刊: JOURNAL OF ORGANIC CHEMISTRY
• 影响因子: 3.6
• 作者: Fernando, E. H. Nisala;Vazquez, Jose Cortes;Wang, Hong
• 通讯作者: Wang, Hong