Radical Migration Reactions Driven by Sustainable Transition-Metal Catalysis

在化学系化学催化项目的支持下，普渡大学的Ming-Yu ngaei教授将研究第一排过渡金属催化，以建立新的化学工艺和促进可持续实践。该项目旨在利用地球上丰富的钴和镍催化剂的反应性，开发新的方法来功能化碳水化合物和其他重要的小分子构建块。该项目旨在进一步了解这些过程中的基本反应性和机制，并开发新的反应，以促进具有潜在社会影响的分子支架的获取。通过与普渡大学科学学院K-12外展团队的合作，该项目还旨在通过向高中生介绍可持续催化概念来激励他们，强调化学在解决全球挑战和促进可持续性方面的作用。通过促进对复杂的自由基迁移相关机制的科学理解，这些研究有可能促进有机合成中相关可持续方法的发展。在此奖项下，Ngai教授及其研究团队将探索钴和镍配合物的基态金属性质与1,2-自由基迁移（RaM）反应性的整合。该项目旨在揭示碳水化合物位点和立体选择性功能化的新途径（碳水化合物化学中的一个重大挑战），并扩大烯丙基羧酸盐的反应范围。通过实验和计算研究的结合，该团队的目标是开发一个催化平台，提供c2 -芳基化反应的轴向和赤道选择性。这些研究有望为镍钴催化剂介导的自由基迁移交叉偶联反应提供新的见解，并因此有助于自由基化学和可持续催化过程的进展。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 the support of the Chemical Catalysis program in the Division of Chemistry, Professor Ming-Yu Ngai of Purdue University will study first-row transition metals in catalysis to establish new chemical processes and foster sustainable practices. This project aims to harness the reactivity of earth-abundant cobalt and nickel catalysts to develop new methods to functionalize carbohydrates and other important small molecule building blocks. The project seeks to both further understanding of the fundamental reactivity and mechanisms in these processes as well as develop new reactions to facilitate access to molecular scaffolds with potential societal impacts. Through collaboration with the College of Science K-12 Outreach team at Purdue, the project also seeks to inspire high school students by introducing them to sustainable catalysis concepts, highlighting chemistry's role in solving global challenges and promoting sustainability. By contributing to the scientific understanding of complex radical migration-related mechanisms, these studies have the potential to catalyze the development of related sustainable methodologies in organic synthesis.Under this award, Professor Ngai and his research team will explore the integration of ground-state metalloradical properties of cobalt and nickel complexes with 1,2-radical migration (RaM) reactivity. The project is set to unveil novel pathways for the site- and stereoselective functionalization of carbohydrates—a significant challenge in carbohydrate chemistry—and to broaden the reaction scope of allyl carboxylates. Through a combination of experimental and computational studies, the team aims to develop a catalytic platform that provides for axial and equatorial selectivity of the C2-arylation reaction. These investigations are expected to provide new insights into radical migratory cross-coupling reactions mediated by nickel and cobalt catalysts, and in so doing contribute to advances in radical chemistry and sustainable catalytic processes.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.