近日，中国科学院化学研究所韩布兴团队报道了串联催化使γ-戊内酯与CO₂和H₂羟基化反应生成己二酸。2025年9月15日出版的《美国化学会志》发表了这项成果。

己二酸是目前从化石资源中提取的一种重要化学物质。

在这项工作中，研究组报告了第一种以生物质衍生的γ-戊内酯（GVL）为原料，用CO₂和H₂生产己二酸的方法。结果发现，在AcOH/H₂O二元溶剂体系中，以I₂助剂的Rh催化剂在相应温度（140℃）下能有效催化该反应。通过实验和DFT研究对反应途径进行了系统而详细的分析。串联一锅工艺法通过将热力学上不利的GVL开环与非常有利的羟基化相结合，实现热力学上的利用，推动整个反应向前生成二酸产物。

该反应包括三个关键步骤：H₂将CO₂还原为CO和H₂O，GVL开环生成反应中间体，中间体与CO和H₂O羟基化。稳定的GVL可以维持高活性中间体的低浓度，防止其加氢副反应，有利于双酸的高选择性。此外，该策略还可以从不同的内酯中获得高收率的各种二酸，二酸的收率可达89%。该方案为两种可再生碳资源和一种绿色还原剂（H₂）可持续合成己二酸开辟了道路。

附：英文原文

Title: Tandem Catalysis Enables the Hydrocarboxylation of γ-Valerolactone with CO2 and H2 to Produce Adipic Acid

Author: Ying Wang, Yanru Zhang, Chenglong Yu, Jia Guo, Jun He, Longbo Zhang, Yanyan Wang, Jianling Zhang, Tianbin Wu, Qingli Qian, Buxing Han

Issue&Volume: September 15, 2025

Abstract: Adipic acid is an industrially important chemical that is currently produced from fossil resources. In this work, we report the first method for the production of adipic acid from biomass-derived γ-valerolactone (GVL) with CO2 and H2. It was discovered that the Rh catalyst with an I2 promoter in a binary solvent system of AcOH/H2O could catalyze the reaction efficiently at an industrially relevant temperature (140 °C). A systematic and detailed analysis of the reaction pathway was conducted via experimental and DFT studies. The tandem one-pot process permits thermodynamic leveraging by coupling the thermodynamically unfavored GVL ring-opening with highly favored hydrocarboxylation, driving the overall reaction forward to diacid products. The reaction involves three key steps, including the reduction of CO2 to CO and H2O by H2, the ring-opening of GVL to reaction intermediates, and the hydrocarboxylation of the intermediates with CO and H2O. The stable GVL can maintain a low concentration of the highly reactive intermediates and prevent their hydrogenation side reactions, which favors the high selectivity of diacids. Moreover, this strategy affords access to various diacids in high yields from different lactones, and the yield of the diacids could reach 89%. This protocol opens the way for the sustainable synthesis of adipic acid from two renewable carbon resources and a green reductant (H2).

DOI: 10.1021/jacs.5c09561

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c09561