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.

通过此奖项，化学催化计划正在为北德克萨斯大学的洪王提供资金，以开发新的催化方法来合成手性分子。手性分子作为不可感染的镜像存在，与左手和右手相同。许多分子，尤其是天然存在的有机化合物和许多药物，是手性的，分子的两种镜像形式通常具有不同的生物学特性。因此，现代有机合成中的一个重要挑战是控制产品的惯用性。 该项目中正在开发的反应旨在提供简洁而多功能的合成途径来构建5元和7元的环系统，并控制了手工的控制，这是当前可用的合成方法的艰难壮举。 Wang博士积极参与共同的努力，以吸引一群学生参加科学，技术，工程和数学（STEM）领域。 她的外展活动以她的研究为基础，并包括针对来自少数学校和高中生的本科生的宣传夏季研究计划，以便在早期对STEM领域的兴趣。 Hong Wang博士和她的研究团队正在通过将Enamine催化与硬金属Lewis酸催化相结合，从而开发新的催化系统。研究了相反的软策略的可行性，以解决合作酸碱催化中涉及的关键酸碱淬灭问题。同样，在研究中，哪些因素会影响原代芳基胺和酮的烯胺形成。 [3+2]和[4+3]的反应是使用合作的磁轴金属刘易斯酸催化来构建5元和7元环系统的反应。此外，还探索了一类新的双金属配合物，可以用作非对称催化中的手性金属路易斯酸催化剂。进行密度功能理论（DFT）计算以了解这些双金属催化剂的结构活性以及[3+2]和[4+3]反应的机制。为了解决该项目的更广泛影响，Wang博士正在积极参与启动外展计划，以向本科和高中生提供夏季研究机会，专注于将女性和少数族裔学生吸引到STEM领域。这一奖项反映了NSF的法定任务，并通过使用该基金会的知识分子功能和广泛的影响来评估NSF的法定任务，并被视为值得的支持。

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