有机化学中的C-H羧基化反应探讨

Discussions on C-H Carboxylation in Organic Chemistry

羧基化反应是有机化学课程教学的一个基本内容(如格氏试剂与CO2的加成及Kolbe-Schmitt反应等),也是工业生产合成羧酸、酯等高附加值化学品的重要方法.然而这些反应需要使用格氏试剂或高压CO2,条件苛刻且底物官能团耐受性窄,在未来有机合成及工业生产中的应用前景有限.为解决这些问题,近年来以二氧化碳作为单碳源的碳-氢直接羧基化反应逐渐兴起,弥补了传统羧基化反应的诸多缺陷,反应的原子/步骤经济性显著提高,更符合“绿色化学”的理念.围绕有机化学课堂教学中的碳氢羧基化反应,分析近期科学研究在经典反应基础上的改进策略,用于丰富课堂教学内容,旨在达到开拓学生视野,引导学生跟进、了解前沿科技进展的目标.

Carboxylation reactions (such as carboxylation of Grignard reagent with CO2 and Kolbe-Schmitt reaction etc.) are basic topics in organic chemistry lessons, and it is also an important method for industrial production of high value-added chemicals such as carboxylic acid and ester. However, these reactions commonly suffer from the drawbacks such as necessity for Grignard reagent, high pressure CO2, harsh reaction conditions or limited substrate scope, which significantly restricts their academic and industrial applications. To settle these problems, the direct C-H carboxylations using carbon dioxide as the C1 source have recently attracted extensive research interest. These reactions conform to the concept of "green chemistry", overcome many drawbacks in traditional carboxylations, and remarkably improved the atomic/step economy. We added introductions in recent research frontiers of direct C-H carboxylation with carbon dioxide in organic lessons, so as to enrich the teaching content and guide students to follow up the frontier progress of carboxylation reactions.