Abstract:
Carboxylation with carbon dioxide (CO2 ) represents one notable methodology to produce carboxylic acids. In contrast to carbon-heteroatom bonds, carbon-carbon bond cleavage for carboxylation with CO2 is far more challenging due to their inherent and less favorable orbital directionality for interacting with transition metals. Here we report a photocatalytic protocol for the deconstructive carboxylation of alkenes with CO2 to generate carboxylic acids in the absence of transition metals. It is emphasized that our protocol provides carboxylic acids with obviously unchanged carbon numbers when terminal alkenes were used. To show the power of this strategy, a variety of pharmaceutically relevant applications including the modular synthesis of propionate nonsteroidal anti-inflammatory drugs and the late-stage carboxylation of bioactive molecule derivatives are demonstrated.
摘要:
用二氧化碳(CO2)的羧化代表了生产羧酸的一种值得注意的方法。与碳-杂原子键相反,用CO2进行羧化的碳-碳键裂解更具挑战性,因为它们固有的且与过渡金属相互作用的轨道方向性较差。在这里,我们报告了在不存在过渡金属的情况下,用CO2对烯烃进行破坏性羧化以产生羧酸的光催化方案。要强调的是,当使用末端烯烃时,我们的方案提供具有明显不变的碳数的羧酸。为了展示这种策略的力量,证明了多种药学相关应用,包括丙酸非甾体抗炎药的模块化合成和生物活性分子衍生物的后期羧化。