Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Aachen, Germany.
Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr, Germany.
Sci Adv. 2023 Feb 3;9(5):eadf2966. doi: 10.1126/sciadv.adf2966.
The carboxylation of nonactivated C─H bonds provides an attractive yet hitherto largely elusive chemical process to synthesize carboxylic acids by incorporation of CO into the chemical value chain. Here, we report on the realization of such a reaction using simple and nonactivated arenes as starting materials. A computationally designed Pd(II) complex acts as organometallic single-component catalyst, and apart from a base, necessary for thermodynamic stabilization of the intermediates, no other additives or coreagents are required. Turnover numbers up to 10 and high regioselectivities are achieved. The potential of this catalytic reaction for "green chemistry" is demonstrated by the synthesis of veratric acid, an intermediate for pharmaceutical production, from CO and veratrol.
非活化 C─H 键的羧化反应为通过将 CO 纳入化学价值链来合成羧酸提供了一种有吸引力但迄今仍难以实现的化学过程。在这里，我们报告了使用简单且非活化的芳烃作为起始原料来实现这种反应。经过计算设计的 Pd(II) 配合物作为有机金属单组分催化剂，除了需要碱来热力学稳定中间体外，不需要其他添加剂或核心试剂。实现了高达 10 的转化率和高区域选择性。通过 CO 和藜芦醇合成香草酸（药物生产的中间体）证明了这种催化反应在“绿色化学”中的潜力。
