CAS: A Rethinking of Borrowing Hydrogen: from Ligand Design to New Reactions and Mechanisms

CAS：借氢的重新思考：从配体设计到新反应和机制

• 批准号: 2102513
• 负责人: Keying Ding
• 金额: $ 17.22万
• 依托单位: Middle Tennessee State University
• 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: 2021-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102513&HistoricalAwards=false
• 关键词: CAS; Rethinking; Borrowing; Hydrogen; Ligand

With the support of the Chemical Catalysis program in the Division of Chemistry, Keying Ding of Middle Tennessee State University will study catalytic reactions that result in the formation of carbon–carbon or carbon–heteroatom bonds. These reactions will be mediated by new earth-abundant metal catalytic systems that utilize the “borrowing hydrogen (BH)” pathway. This BH pathway is environmentally friendly and atom- and process-efficient in producing value-added chemicals while producing water as the sole byproduct. Structure-reactivity correlations will be studied in an effort to glean critical information on how these catalysts facilitate this chemistry at the molecular level. The results will be used to direct catalyst development toward new and challenging reactions. This project will offer research experiences for students at the interface of synthetic inorganic chemistry, organic chemistry, and catalysis. The educational activities include efforts to enhance the participation of undergraduate students from underserved groups and low-income or first-generation families, participation in a summer research camp, and the integration of the funded research into teaching laboratories. The broader impacts of the research and educational activities will assist in the creation of a more diverse and educated workforce in the chemical sciences.Dr. Keying Ding and her research team at Middle Tennessee State University will study new base-transition metal catalysts to address emerging challenges in catalytic reactions that utilize the “borrowing hydrogen” mechanistic pathway. A new family of bifunctional ligands that feature reactive pendant arms that potentially promote hydrogen transfer reactions via metal-ligand cooperativity, and that contain rigid ligand scaffolds to provide stability, will be synthesized and characterized. The catalytic activities of the base transition-metal complexes will be determined with a focus on (i) establishing an in-depth understanding of the BH catalytic process, (ii) eliminating the dependence on the use of excess strong base in the BH reactions, and (iii) improving the product selectivity. New concepts and insights on the use of earth-abundant metals in place of precious transition metals for BH and related transformations are expected to arise from these studies to help guide the development of future catalysts.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.

在化学系化学催化项目的支持下，中田纳西州立大学的丁克英将研究导致碳-碳或碳-杂原子键形成的催化反应。这些反应将由地球上丰富的新金属催化系统介导，该系统利用“借氢（BH）”途径。该 BH 途径在生产增值化学品的同时生产水作为唯一的副产品，具有环境友好性、原子效率和工艺效率。 将研究结构-反应性相关性，以收集有关这些催化剂如何在分子水平上促进这种化学反应的关键信息。研究结果将用于指导催化剂开发新的、具有挑战性的反应。该项目将为学生提供合成无机化学、有机化学和催化领域的研究经验。教育活动包括努力加强来自服务不足群体和低收入或第一代家庭的本科生的参与，参加夏令营，以及将资助的研究纳入教学实验室。研究和教育活动的更广泛影响将有助于在化学科学领域培养更加多样化和受过教育的劳动力。 Keying Ding 和她在中田纳西州立大学的研究团队将研究新型碱过渡金属催化剂，以解决利用“借氢”机制途径的催化反应中出现的新挑战。将合成和表征一个新的双功能配体家族，其特征是具有反应性侧臂，可通过金属-配体协同作用促进氢转移反应，并且包含刚性配体支架以提供稳定性。碱性过渡金属配合物的催化活性将重点确定（i）建立对BH催化过程的深入了解，（ii）消除BH反应中对使用过量强碱的依赖，以及（iii）提高产物选择性。这些研究预计将产生关于使用地球丰富的金属代替贵重过渡金属进行 BH 和相关转化的新概念和见解，以帮助指导未来催化剂的开发。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力优点和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Switching between borrowing hydrogen and acceptorless dehydrogenative coupling by base transition-metal catalysts

• DOI: 10.1016/j.tet.2021.132451
• 发表时间: 2021-09
• 期刊: Tetrahedron
• 影响因子: 2.1
• 作者: Keying Ding