基于自由基机理光催化羧基化反应研究进展

Recent Advances in Photocatalytic Carboxylation Based on Free Radical Process

二氧化碳(CO_(2))是一种对气候变化有重要影响的温室气体.从化学角度考虑,作为“碳一(C1)”资源,CO_(2)具有储量丰富、廉价易得及无毒可再生等特点.通过化学转化的方式将CO_(2)资源化利用,并用于合成高附加值化学品,是服务国家重大战略需求的重要方式,也是响应国家2030年“碳达峰”与2060年“碳中和”目标的重要举措.有机光催化能够利用光能激发电子转移,引发化学键的断裂和重组,促进反应的进行,具备条件温和、绿色清洁以及选择性高等优点.CO_(2)资源化利用与有机光催化相结合所形成的光催化羧基化反应体系,能够为羧基化反应的研究提供新思路.系统阐述了两种光催化羧基化反应,即以碳负离子为关键中间体和以CO_(2)自由基负离子为关键中间体的羧基化反应.

Carbon dioxide(CO_(2))exerts a significant influence on climate change as a potent greenhouse gas.From a chemical standpoint,CO_(2) serves as an abundant and cost-effective“carbon one(C1)”resource with non-toxicity,renewability,and easy obtainability.The utilization of CO_(2) for synthesizing high-value-added chemicals represents an important avenue for addressing national strategic requirements and aligning with China’s objectives of peaking carbon emissions by 2030 and achieving carbon neutrality by 2060.Organic photocatalysis can harness light energy to induce electron transfer in organic chemical reactions,facilitating bond cleavage and recombination processes.This approach offers advantages such as mild reaction conditions,environmental friendliness and exceptional selectivity.By integrating CO_(2) resource utilization with organic photocatalysis,novel opportunities arise for enriching carboxylation reactions.Two distinct types of photocatalytic carboxylation reactions,those involving carbon anions as pivotal intermediates and those featuring CO_(2) radical anions as key intermediates,are systematically elucidated.