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.

在化学系化学合成项目的支持下，亚利桑那大学的 Thomas Gianetti 和他的研究小组正在开发制造稳定碳正离子（碳原子上带有正电荷的有机分子）的方法，这些碳正离子与电子相连丰富的基团，可以作为催化剂或过渡金属中心的配体，具有双重功能，正在研究这些化合物，以确定它们是否比使用缺电子硼中心而不是碳阳离子的更传统的系统提供更大的可调性和耐受性。此外，Gianetti 博士和他的研究团队正在测试这些两亲性配位作为过渡金属配合物的配体，与金属中心协同作用，以激活小分子形成新的成键模式。这些研究也将为有机化学家提供新的方法。制造增值化合物，并有望为如何利用这些新的碳阳离子化合物进入新的化学空间以支持合成化学提供基本见解。Gianetti 博士还致力于改善科学家和科学家之间的沟通。培养政策制定者，是与法学院的联合课程，旨在培养一批能够跨越学科障碍讨论环境政策的本科生。虽然碳正离子的物理有机性质已被仔细研究，但人们对这些化合物的用途知之甚少。合成化学中过渡金属催化剂的催化剂和配体正在开发碳阳离子受阻路易斯对，并测试它们对多聚甲醛和烯烃的亲核加成反应活性。将制备和研究这些催化剂的类似物，以用于催化不对称转化。将进一步探索将这些两亲性羧基掺入配体支架中，以支持烯丙醇和 NO2 等小分子的协同活化。这些活动将协同地提供重要的训练。为亚利桑那大学不同群体的研究生和本科生提供合成化学和有机金属概念。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。