Ogbu Ikechukwu Martin, Kurtay Gülbin, Badufle Margaux, Robert Frédéric, Lopez Carlos Silva, Landais Yannick
Institute of Molecular Sciences (ISM), Univ. Bordeaux, CNRS, UMR-5255, 351 Cours de la Libération, 33400, Talence, France.
University of Ankara, Department of Chemistry, Faculty of Science, 06800, Ankara, Turkey.
Chemistry. 2023 Mar 13;29(15):e202202963. doi: 10.1002/chem.202202963. Epub 2023 Feb 24.
The PIDA-mediated oxidative decarboxylation of oxamic acids in the presence of alcohols is shown to afford the corresponding urethanes under thermal conditions. Computational and experimental mechanistic exploration allows to rationalize the different reactivity of PIDA as compared to related cyclic BI-OAc and highlights the importance of the enhanced acidity of the proton in the carbamoyl radical intermediate.
研究表明,在醇存在的情况下,PIDA介导的草氨酸氧化脱羧反应在热条件下可生成相应的氨基甲酸酯。通过计算和实验进行的机理探索,能够解释PIDA与相关环状BI-OAc相比具有不同反应活性的原因,并突出了氨基甲酰基自由基中间体中质子酸度增强的重要性。