ABSTRACT

Carbon dioxide (CO₂) utilization for the production of fuels and energy-rich chemicals is one of the attractive topics of research in modern-day chemistry. The main barriers in the CO₂ utilization include: 1) the cost associated in CO₂ capture, separation, purification, and transportation; 2) higher energy demand for conversion due to its higher kinetic and thermodynamic stability; 3) the lack of socio-economical driving forces. Valorization of CO₂ has been realized as a viable option for the mitigation of CO₂ as well as to create new business opportunities. Carbon dioxide is a nontoxic, renewable, and abundant C1 source; whereas carboxylation of olefins to carboxylic acids represents one of the most important transformations owing to the broad applicability of these chemicals in various domains, such as water-absorbing polymers, preservatives of food, fertilizers, building blocks for the manufacturing of cosmetics, soaps, detergents, rubbers, dyes, animal feed, plastics, agrochemicals and pharmaceuticals. The present review mainly focuses on the recent advances in the transition metal-catalyzed carboxylation of the olefins by using carbon dioxide as a feedstock. Firstly, the hydrocarboxylation or direct carboxylation using coordination complexes of transition metals such as rhodium, copper, cobalt, nickel, ruthenium, iron, palladium, and zirconium have been discussed in detail. In the next section, the hetero carboxylation reactions, for example, boracarboxylation, silacarboxylation, carbocarboxylation, thiocarboxylation and dicarboxylation have been presented to explore the wider scope of CO₂ utilization for carboxylation reactions. Lastly, the carboxylation of dienes and difunctionalization reactions have been discussed. Further, the recent trends and key challenges in the use of CO₂ as a carbxylating agent for carboxylation reactions have been described.

摘要

二氧化碳 (CO ₂ ) 用于生产燃料和富含能量的化学品是现代化学研究的热门课题之一。_{CO 2}利用的主要障碍包括：1）与CO ₂捕获、分离、纯化和运输相关的成本；2）由于其更高的动力学和热力学稳定性，转化所需的能量更高；3）缺乏社会经济驱动力。CO ₂的增值已成为减缓 CO _{2的可行选择}以及创造新的商业机会。二氧化碳是一种无毒、可再生且丰富的 C1 源；而烯烃羧化为羧酸是最重要的转化之一，因为这些化学物质在各个领域具有广泛的适用性，例如吸水性聚合物、食品防腐剂、化肥、化妆品、肥皂、洗涤剂制造的基石、橡胶、染料、动物饲料、塑料、农用化学品和药品。本综述主要关注以二氧化碳为原料的过渡金属催化烯烃羧化的最新进展。首先，使用铑、铜、钴、镍、钌、铁、钯等过渡金属的配位络合物进行加氢羧化或直接羧化，和锆已经详细讨论过。在下一节中，介绍了杂羧基化反应，例如硼羧基化、硅烷羧基化、碳羧基化、硫代羧基化和二羧基化，以探索更广泛的 CO₂用于羧化反应。最后，讨论了二烯的羧化和双官能化反应。此外，已经描述了使用 CO ₂作为羧化剂进行羧化反应的最新趋势和主要挑战。