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

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碳氢键的直接羰基化和碳氢键的直接双羰基化。催化被广泛认为是一个重要的工具，在不断努力减少浪费和努力更有效地利用化学原料。所提出的实验方法将由计算化学补充和指导，以协助确定所提出的催化循环中基本步骤的局限性，并为以铼为中心金属制备改进催化剂的合成选择提供信息。该计划将可持续化学和催化的概念整合到研究生和本科生，博士后助理和高中生的培训和教学中。该研究项目结合了机械化学的重要元素，包括高中和本科水平的计算方法的整合，以及将催化和可持续化学纳入本科教学实验室项目。为达致该项目的研究目标，艾森教授及其团队将致力以下具体目标：(i)研究醋酸铼配合物对碳氢键的活化作用；（ii）了解与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及其他碳氢功能化反应的铼催化剂。这些研究将探讨协同的金属-去质子化反应机制是否为铼介导的C-H活化反应提供了可行的途径。追求铼催化的双羰基化反应对这些研究特别感兴趣，因为这种转化相对不常见，但如果更好地理解，可能会产生很大的影响。目标产品有望成为许多天然产品和具有重要生物活性的药物中重要的化学组成部分。再介导反应的可行性将进行计算和实验研究。鉴于所描述的不同寻常的反应途径以及对羰基插入金属-酰基键的长期兴趣，该研究有望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见解。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 (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.