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.

在化学催化计划中，田纳西州立大学的化学催化计划的支持将研究催化反应，从而导致形成碳 - 碳或碳 - 透明质酸键。这些反应将由利用“借用氢（BH）”途径的新型地球丰富的金属催化系统介导。该BH途径在产生增值化学物质的同时，在产生水作为唯一的副产品的同时，在产生增值化学物质方面具有环境友好和原子和过程效率。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支持该化学的关键信息。结果将用于将催化剂开发引向新的和挑战反应。该项目将在合成无机化学，有机化学和催化的界面上为学生提供研究经验。教育活动包括加强来自服务不足的团体和低收入或第一代家庭的本科生参与的努力，参与夏季研究营，以及资助的教学实验室研究的整合。研究和教育活动的更广泛的影响将有助于在化学科学中创建更多样化和受过教育的劳动力。在田纳西州立大学的键盘和她的研究团队中，将研究新的碱基过渡金属催化剂，以应对利用“借用氢”机械途径的催化反应的新兴挑战。一个新的双功能配体系列，具有反应性吊坠臂，可以通过金属配体配位促进氢转移反应，并包含刚性配体支架以提供稳定性，并将合成和表征。基础过渡金属复合物的催化活性将以（i）为重点（i）确定对BH催化过程的深入了解，（ii）消除对BH反应中过量强碱的依赖，（iii）提高产品选择性。关于使用珍贵的金属代替宝贵的过渡金属的新概念和见解，这些研究预计将从这些研究中产生，以帮助指导未来的催化剂。该奖项反映了NSF的法定任务，并已通过评估基金会的知识和更广泛的影响来诚实地认为，通过评估诚实的支持。

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