The catalytic formation of cyclic organic carbonates (COCs) using carbon dioxide (CO₂) as a renewable carbon feed stock is a highly vibrant area of research with an increasing amount of researchers focusing on this thematic investigation. These organic carbonates are highly useful building blocks and nontoxic reagents and are most commonly derived from CO₂ coupling reactions with oxirane and dialcohol precursors using homogeneous catalysis methodologies. The activation of suitable reaction partners using catalysis as a key technology is a requisite for efficient CO₂ conversion as its high kinetic stability poses a barrier to access functional organic molecules with added value in both academic and industrial laboratories. Although this area of science has been flourishing for at least a decade, in the past 2–3 years, significant advancements have been made to address the general reactivity and selectivity issues that are associated with the formation of COCs. Here, we present a concise overview of these activities with a primary focus to highlight the most important progress made and the opportunities that catalysis can bring about when the synthesis of these intermediates is optimized to a higher level of sophistication. The attention will be limited to those cases in which homogeneous metal-containing systems have been employed because they possess the highest potential for directed organic synthesis using CO₂ as molecular building block. This review discusses examples of exceptional reactivity and selectivity, taking into account the challenging nature of the substrates that were involved, and mechanistic understanding guiding the optimization of these protocols is also highlighted.

The conversion of carbon dioxide (CO ₂ ), an abundant renewable carbon reagent, into chemicals of academic and industrial interest is of imminent importance to create a higher degree of sustainability in chemical processing and production.

Green upgrading of renewablesviamethylations and carboxymethylations with non-toxic dimethyl carbonate (DMC).

The efficient and highly selective formation of a wide range of (hetero)cyclic cis‐diol scaffolds using aminotriphenolate‐based metal catalysts is reported. The key intermediates are cyclic carbonates, which are obtained in high yield and with high levels of diastereo‐ and chemoselectivity from the parent oxirane precursors and carbon dioxide. Deprotection of the carbonate structures affords synthetically useful cis‐diol scaffolds with different ring sizes that incorporate various functional groups. This atom‐efficient method allows the simple construction of diol synthons using inexpensive and accessible precursors and green metal catalysts and showcases the use of CO₂ as a temporary protecting group.

The challenging coupling of highly substituted terpene oxides and carbon dioxide into bio‐based cyclic organic carbonates catalyzed by Al(aminotriphenolate) complexes is reported. Both acyclic as well as cyclic terpene oxides were used as coupling partners, showing distinct reactivity/selectivity behavior. Whereas cyclic terpene oxides showed excellent chemoselectivity towards the organic carbonate product, acyclic substrates exhibited poorer selectivities owing to concomitant epoxide rearrangement reactions and the formation of undesired oligo/polyether side products. Considering the challenging nature of these coupling reactions, the isolated yields of the targeted bio‐carbonates are reasonable and in most cases in the range 50–60 %. The first crystal structures of tri‐substituted terpene based cyclic carbonates are reported and their stereoconnectivity suggests that their formation proceeds through a double inversion pathway.