CAS: Catalytic Carbonylation and C-H functionalization Reactions with Rhenium Complexes

CAS：铼配合物的催化羰基化和 C-H 官能化反应

• 批准号: 2154878
• 负责人: Elon Ison
• 金额: $ 50万
• 依托单位: North Carolina State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-06-15 至 2025-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154878&HistoricalAwards=false
• 关键词: CAS; Catalytic; Carbonylation; functionalization; Reactions

With the support of the Chemical Catalysis (CAT) and the Chemical Synthesis (SYN) Programs in the Division of Chemistry, Professor Elon Ison of North Carolina State University will study the direct carbonylation of C–H bonds by transition metal catalysts and the direct double carbonylation of C–H bonds. Catalysis is widely recognized as an important tool in the continued effort to minimize waste and in the effort to utilize chemical feedstocks more efficiently. The proposed experimental approach will be complemented and guided by computational chemistry to assist in identifying the limitations of elementary steps in the proposed catalytic cycles and to inform synthetic choices for the preparation of improved catalysts using rhenium as the central metal. The program integrates the concepts of sustainable chemistry and catalysis into the training and teaching of graduate and undergraduate students, postdoctoral associates, and high school students. The research program incorporates important elements of mechanistic chemistry including the integration of computational methods at the high school and undergraduate levels, and the incorporation of catalysis and sustainable chemistry into undergraduate teaching laboratory programs. To achieve research goals of the project, Professor Ison and his team will pursue the following specific aims: (i) examination of the activation of C–H bonds by rhenium (III) acetate complexes, (ii) understanding mono- and double carbonylation reactions with rhenium complexes, and (iii) development of a rhenium catalyst for double and mono-carbonylation reactions and other C–H functionalization reactions. These studies will probe whether a concerted metalation-deprotonation reaction mechanism provides a viable pathway for the rhenium-mediated C–H activation reaction. The pursuit of rhenium-catalyzed double carbonylation reactions is of particular interest to these studies as this transformation is relatively uncommon, but potentially of high impact, if better understood. The target products are expected to be important chemical building blocks present in many natural products and pharmaceuticals that display important biological activity. The viability of the Re-mediated reactions will be investigated computationally and experimentally. Given the unusual reaction pathways described and the longstanding interest in carbonyl insertion into metal-acyl bonds, this research is expected to be of broad interest to the inorganic and organometallic chemistry communities and will likely offer insight into the design of new catalytic systems.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（CAT）和化学合成（SYN）项目的支持下，北卡罗莱纳州立大学的Elon Ison教授将研究过渡金属催化剂对C-H键的直接羰基化和C-H键的直接双羰基化。催化被广泛认为是持续努力减少废物和更有效地利用化学原料的重要工具。所提出的实验方法将得到计算化学的补充和指导，以帮助确定所提出的催化循环中基本步骤的局限性，并为使用铼作为中心金属制备改进催化剂的合成选择提供信息。该项目将可持续化学和催化的概念融入到研究生和本科生、博士后和高中生的培训和教学中。该研究计划融合了机械化学的重要元素，包括高中和本科阶段计算方法的整合，以及将催化和可持续化学纳入本科教学实验室计划。为了实现该项目的研究目标，Ison教授和他的团队将追求以下具体目标：（i）检查乙酸铼（III）配合物对C-H键的活化作用，（ii）了解铼配合物的单羰基化和双羰基化反应，以及（iii）开发用于双羰基化和单羰基化反应以及其他C-H官能化反应的铼催化剂。这些研究将探讨协同金属化-去质子化反应机制是否为铼介导的 C-H 活化反应提供可行的途径。这些研究对铼催化的双羰基化反应特别感兴趣，因为这种转化相对不常见，但如果更好地理解的话，可能会产生很大的影响。目标产品预计将成为许多天然产物和药物中存在的重要化学结构单元，具有重要的生物活性。重新介导的反应的可行性将通过计算和实验进行研究。鉴于所描述的不寻常的反应途径以及长期以来对羰基插入金属酰基键的兴趣，这项研究预计将引起无机和有机金属化学界的广泛兴趣，并可能为新催化系统的设计提供深入的见解。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进行评估，被认为值得支持。