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

通过这个奖项，化学催化项目资助北德克萨斯大学的王宏博士开发新的催化方法来合成手性分子。手性分子以不可重叠的镜像形式存在，这与左手和右手的区别是一样的。许多分子，特别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，现代有机合成的一个重要挑战是控制产物的手性。在这个项目中开发的反应旨在提供简洁和通用的合成途径来构建5元和7元环体系，并控制手性，这是目前可用的合成方法的一个困难的壮举。王博士积极参与共同努力，吸引不同群体的学生进入科学、技术、工程和数学（STEM）领域。她的推广活动建立在她的研究基础上，包括针对少数民族学校和高中生的本科生的推广暑期研究项目，以在早期阶段建立对STEM领域的兴趣。王红博士和她的研究团队正在通过将烯胺催化与硬金属路易斯酸催化相结合来开发新的催化系统。研究了逆向软硬策略解决酸碱协同催化中酸碱猝灭问题的可行性。同时，哪些因素会影响原芳胺和酮形成烯胺也在研究中。采用胺-硬金属路易斯酸协同催化，建立了[3+2]和[4+3]反应，构建了5元和7元环体系。此外，还探索了一类新的双金属配合物作为手性硬金属路易斯酸催化剂用于不对称催化。通过密度泛函理论（DFT）计算了解了这些双金属催化剂的构效关系以及[3+2]和[4+3]反应的机理。为了解决这个项目更广泛的影响，王博士积极参与外展计划，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民族学生进入STEM领域。该奖项反映了美国国家科学基金会的法定使命，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 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.