Recent Advances in Using Carbon Dioxide as a Carbonyl Source for Carbonylation Reactions

Carbon dioxide (CO 2 ) is an abundant, low-cost, and non-toxic C1 building block, and its valorization plays a pivotal role in achieving the goal of carbon neutrality. The incorporation of CO 2 as a carbonyl source into organic molecules is a key step in synthesizing high-value chemicals. However, the thermodynamic stability and kinetic inertness of CO 2 pose significant challenges to its direct carbonylation. In recent years, the research focus has shifted from single catalytic systems to more advanced strategies such as combined catalysis and energy-driven approaches, which have shown great potential in CO 2 carbonylation reactions. Among these, the reverse water-gas shift (RWGS) strategy effectively integrates into classical transition metal catalysis by converting CO 2 in situ into highly reactive CO. Meanwhile, electro-thermal and photo-thermal coupling methods offer effective means to overcome reaction energy barriers through the synergistic effect of multiple energy inputs. This review systematically summarizes the latest advances in CO 2 carbonylation reactions across three catalytic modes: thermal catalysis, electrothermal catalysis, and photothermal catalysis. It highlights the core advantages and current progress of advanced catalytic strategies. Moreover, it elaborates on the reaction pathways and mechanisms, with a focus on different substrate-based reaction systems, such as alkene carbonylation, alkyne carbonylation, amine carbonylation, alcohol/ether carbonylation, and other types. Finally, the review outlines the main challenges and outlook for future research in this field. By reviewing thermal, electro-thermal, and photo-thermal catalytic strategies, this article highlights their application in CO 2 -based carbonylation (e.g., of alkenes, alkynes, amines, alcohols) to facilitate the sustainable synthesis of high value chemicals.