The production of fine chemicals using CO2 as C1 building block through inexpensive heterogeneous catalysts with high efficiency under low pressure is challenging. Herein we propose for the first time the utilization of a multifunctional heterogeneous zinc‐modified HZSM‐5 (ZnHZSM‐5) catalyst for upgrading CO2 by incorporation into cyclic carbonates from CO2 and epoxides. Owing to the nice surface properties such as abundant Lewis acid, Brønsted acid and Lewis base sites, large surface area, and plenty of micropores, CO2 could be concentrated and well activated in ZnHZSM‐5 verified by CO2‐TPD, TG‐MS, etc. Meanwhile, the epoxides were also activated through metal center and hydrogen bond. Therefore, the reaction can easily assemble at the catalyst interface and show exceptional performance, affording the aimed products with high yield of up to 99% in the presence of commercial tetra‐n‐propylammonium bromide (90% in kilogram scale with 0.004 mol% ZnHZSM‐5 and 0.015 mol% nPr4NBr).

It is promising and challenging to achieve the effective construction of carbonates using CO2 and a non-noble metal catalyst. Herein, selective catalytic conversion of CO2 and switchable alcohol candidates to produce linear or cyclic carbonates and α-hydroxy ketones via effective zinc catalyst was developed. A series of primary alcohols and cyclohexanol, 1,2-diols, and water can serve as nucleophiles to give alkyl or aryl 2-substituted-3-oxobutan-2-yl carbonates, substituted 1,3-dioxolan-2-ones, 3-substituted 3-hydroxybutan-2-ones, respectively with excellent selectivity and high yields.

In recent years increasing attention has been given to the efficacious synthesis of organic carbonates from sustainable CO2. The carboxylation/hydration reaction of alcohols with CO2 stands out for its environmentally friendly and economic features. However, it faces several substantial challenges such as thermodynamic limitations, low catalytic efficiency, and product selectivity. In this article, recent advances in the development of catalytic methods for the synthesis of organic carbonates through carboxylation/hydration reaction of alcohols with CO2 are summarized. Catalytic schemes (metal and metal‐free catalysis), water‐dehydration strategies, and catalytic mechanisms are also discussed in detail. The review covers the carbonylation cyclization of various alcohols and the equivalent of CO2, i.e. urea. Finally, an overview is provided of the recent breakthrough in the development of thermodynamically favorable processes involving alcohols and CO2. © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd.

It remains a great challenge to convert CO2 into high value‐added products under ambient pressure. Herein, an efficient dual‐component catalytic system, i. e., Ag(I)/(C2H5)4NCl was developed for the synthesis of various β‐oxopropylcarbamates via one‐pot three‐component coupling of CO2, secondary amines and propargylic alcohols under atmospheric pressure. Besides, the strategy avoided the use of any additional ligand and basic species, and excellent selectivity was achieved with a yield of up to 98%. Additionally, 13Ccarbonyl‐labeled and control experiments were carefully performed to demonstrate the mechanism. Notably, this new method was also applied efficiently in quantitative chemical fixation of CO2, i. e., the two‐component reaction of propargylic alcohols and ammonium carbamates.