Development of Stable Carbocations for Lewis Acid-Assisted Transformations

用于路易斯酸辅助转化的稳定碳阳离子的开发

• 批准号: 2102034
• 负责人: Thomas Gianetti
• 金额: $ 47.5万
• 依托单位: University of Arizona
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-08-01 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102034&HistoricalAwards=false
• 关键词: Development; Stable; Carbocations; Lewis; Acid

With the support of the Chemical Synthesis Program in the Division of Chemistry, Thomas Gianetti of the University of Arizona and his research group are developing ways to make stable carbocations – organic molecules that have a positive charge on a carbon atom – that are attached to electron-rich groups and can serve as catalysts, or ligands for transition metal centers, with dual functionalities. These compounds are being studied to determine if they provide greater tunability and tolerance than more traditional systems that use electron-deficient boron centers instead of carbocations. In addition, Dr. Gianetti and his research team are testing these ambiphilic carbocations as ligands for transition metal complexes to work synergistically with the metal center to activate small molecules toward new modalities for bond formation. These studies will also provide new ways for organic chemists to make value-added compounds and are expected to provide fundamental insight into how these new carbocationic compounds can be used to access new chemical space to support of synthetic chemistry. Dr. Gianetti is also committed to improving communication between scientists and policymakers and is developing a joint course with the College of Law to build a cohort of undergraduate students that can discuss environmental policy across disciplinary barriers.While the physical organic properties of carbocations have been carefully studied, little is known about the use of these compounds as catalysts and ligands for transition metal catalysts in synthetic chemistry. Thomas Gianetti and his research team are developing carbocationic frustrated Lewis pairs and testing their reactivity for nucleophilic additions to paraformaldehyde and alkenes. In addition, helically chiral analogues of these catalysts will be prepared and investigated for catalytic asymmetric transformations. Incorporation of these ambiphilic carbocations into ligand scaffolds is to be further explored to support the cooperative activation of small molecules such as allylic alcohols and NO2. These activities will synergistically provide important training in synthetic chemistry and organometallic concepts for a diverse group of graduate and undergraduate students at the University of Arizona.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.

在化学合成计划中的化学划分下，亚利桑那大学及其研究小组的Thomas Gianetti正在开发制造稳定碳酸化的方法 - 在碳原子上具有正电荷的有机分子 - 这些分子与电子富含电子群相连，并可以作为催化剂或用于过渡金属中心的物品，并带有与单位功能相关的物质。这些化合物正在研究，以确定它们是否提供了使用电子缺陷硼中心而不是碳化的更传统的系统。此外，Gianetti博士和他的研究团队正在测试这些Ambiphilic碳水化合物作为过渡金属配合物的配体，以与金属中心协同工作，以激活小分子，以朝着新的形成键形成的新方式。这些研究还将为有机化学家提供新的方法来制作增值化合物，并有望提供基本的见解，以了解如何使用这些新的碳化合物来获取新的化学空间以支持合成化学。 Gianetti博士还致力于改善科学家与政策制定者之间的沟通，并正在与法律学院开发联合课程，以建立一群本科生，这些学生可以在跨学科障碍之间讨论环境政策。虽然已经仔细研究了碳酸的物理组织特性，但对这些化合物作为催化剂和配体在合成化学中的过渡金属催化剂的使用知之甚少。 Thomas Gianetti和他的研究团队正在开发碳分配式挫败刘易斯的配对，并测试了它们对核脱氢和烷烃的反应性。此外，将准备并研究这些催化剂的螺旋性手性类似物，以进行催化不对称转化。应进一步探索这些抗硫碳酸化的配体支架中，以支持小分子（例如Allic醇和NO2）的合作激活。这些活动将在亚利桑那大学的一群研究生和本科生的综合化学和有机概念方面协同培训。这项奖项反映了NSF的法定任务，并被认为是通过基金会的知识分子优点和更广泛的影响审查标准通过评估来获得支持的。