Lumbreras-Teijeiro Alejandro, Oliver-Meseguer Judit, Leyva-Pérez Antonio
Instituto de Tecnología Química (UPV-CSIC), Universitat Politècnica de València-Agencia Estatal Consejo Superior de Investigaciones Científicas, Avda. de los Naranjos s/n, 46022, Valencia, Spain.
Chempluschem. 2025 Jul;90(7):e202500203. doi: 10.1002/cplu.202500203. Epub 2025 May 12.
The design of cascade reactions in synthetic programs is of interest, particularly if the individual steps involve catalyzed reactions, and simple and highly available molecules such as carbon dioxide (CO), water (HO), and dihydrogen (H) are employed. Herein, a three-step sequential reaction is shown from epoxides to dehydrogenated diols, catalyzed by a combination of commercially available ionic liquids and supported Pt species on charcoal (Pt/C) in low amounts (<0.05 mol%). The process involves first carbonation of epoxides with CO, followed by the opening of the carbonate with HO, and then an acceptor-less dehydrogenation reaction of the resulting diol to release H. The inclusion of this last step in the one-pot synthesis of diols from epoxides is, to the knowledge, unprecedented. Reactive and kinetic experiments for each individual step reveal the key role of CO to avoid epoxide polymerizations and enable the synthesis of a clean diol for the final dehydrogenation reaction.
合成程序中级联反应的设计备受关注，特别是当各个步骤涉及催化反应，并且使用诸如二氧化碳（CO）、水（HO）和氢气（H₂）等简单且易于获取的分子时。在此，展示了一个从环氧化物到脱氢二醇的三步连续反应，该反应由市售离子液体和负载在木炭上的少量铂物种（Pt/C，<0.05 mol%）组合催化。该过程首先是环氧化物与CO进行碳酸化反应，接着是碳酸酯与HO发生开环反应，然后是所得二醇进行无受体脱氢反应以释放H₂。据了解，在从环氧化物一锅法合成二醇的过程中包含最后这一步是前所未有的。对每个单独步骤进行的反应性和动力学实验揭示了CO在避免环氧化物聚合以及使最终脱氢反应能够合成纯净二醇方面的关键作用。
