Beijing National Laboratory for Molecular Sciences, Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science, NMPA Key Laboratory for Research and Evaluation of Radiopharmaceuticals, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.
Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
Nat Commun. 2022 Nov 19;13(1):7112. doi: 10.1038/s41467-022-34833-1.
The preparation of high value-added boronic acids from cheap and plentiful carboxylic acids is desirable. To date, the decarboxylative borylation of carboxylic acids is generally realized through the extra step synthesized redox-active ester intermediate or in situ generated carboxylic acid covalent derivatives above 150 °C reaction temperature. Here, we report a direct decarboxylative borylation method of carboxylic acids enabled by visible-light catalysis and that does not require any extra stoichiometric additives or synthesis steps. This operationally simple process produces CO and proceeds under mild reaction conditions, in terms of high step economy and good functional group compatibility. A guanidine-based biomimetic active decarboxylative mechanism is proposed and rationalized by mechanistic studies. The methodology reported herein should see broad application extending beyond borylation.
从廉价且丰富的羧酸制备高附加值的硼酸酯是人们所期望的。迄今为止，羧酸的脱羧硼化通常是通过额外步骤合成氧化还原活性酯中间体或在 150°C 以上的反应温度原位生成羧酸共价衍生物来实现的。在这里，我们报道了一种可见光催化的羧酸直接脱羧硼化方法，该方法不需要任何额外的化学计量添加剂或合成步骤。该操作简单的过程在温和的反应条件下生成 CO，并具有高经济性和良好的官能团兼容性。通过机理研究提出并合理化了基于胍的仿生活性脱羧机理。本文报道的方法应该会在硼化以外的领域得到广泛应用。
