Synthesis of Bio-Derived Cyclic Carbonates from Renewable Resources

Abstract

The coupling reaction of carbon dioxide and terminal, internal, and highly substituted epoxides derived from renewable resources such as furfural, limonene, carvone, carvyl acetate, terpinen-4-ol, or ionone leads to the synthesis of new bioderived cyclic carbonates using an efficient aluminum catalyst under mild and solvent-free reaction conditions. Interestingly, the synthesis of highly substituted bioderived cyclic carbonates can occur with excellent diastereoselectivity, obtaining in some cases one diastereoisomer as the major product. The X-ray crystal structures of two enantiomerically pure carvonebased cyclic carbonates are reported.

Synthesis of Bio‐Based Cyclic Carbonates Using a Bio‐Based Hydrogen Bond Donor: Application of Ascorbic Acid to the Cycloaddition of CO2 to Oleochemicals

“…Use of CaI 2 /PPh 3 /dicyclohexyl‐functionalized 18‐crown‐6 ether (DCFCE) led to carbonation of EMO at low temperature (45 °C) under 10 bar CO 2 pressure . Similarly, efficient Al(III) and La(III) complexes were reported as Lewis acids for carbonation of limonene monoxide under mild conditions (70–85 °C, 10 bar CO 2 ). A different way to accelerate catalytic reactions is by means of organocatalytic hydrogen bond donors (HBDs) .…”

Efficient Synthesis of Cyclic Carbonates from Unsaturated Acids and Carbon Dioxide and their Application in the Synthesis of Biobased Polyurethanes

“…Given the excellent catalytic performance and the wide substrate scope shown by lanthanum complex 1 for the synthesis of cyclic carbonates from CO 2 and both terminal and internal epoxides, [11f] we investigated the use of complex 1 as catalyst for the preparation of a set of bio‐based cyclic carbonates, which have been barely studied (Figure 1). [11i,13] …”

“…Our research group has great expertise in the synthesis of new heteroscorpionate rare‐earth metal complexes which have shown to be highly efficient catalysts in ring‐opening polymerization (ROP) and hydroelementation processes [17] . Additionally, we have previously reported the use of heteroscorpionate metal complexes as efficient catalysts for cyclic carbonate formation [11i,18] . For instance, single‐component aluminum catalysts have shown to be efficient catalysts for the preparation of various cyclic carbonates using a low catalyst loading (0.25–2.50 mol %) under relatively mild reaction conditions (70–90 °C and 10 bar pressure) [18b,c] .…”

“…Recently, research groups have focused their attention towards the synthesis of bio‐based cyclic‐ or polycarbonates derived from renewable feedstocks which is an interesting and promising challenge [11–14] . These bio‐derived substrates can be obtained from terpenes, [11] fatty acids [12] and furan derivatives, amongst others, [11f,i,13] and have shown applications in sustainable chemistry and polymer science [14]…”

Unlocking the Potential of Substrate‐Directed CO2 Activation and Conversion: Pushing the Boundaries of Catalytic Cyclic Carbonate and Carbamate Formation

“…[5] However, the lower reactivity of more bulky epoxides has been recently catching growing attention of the community for various reasons. First, the conversion of internal epoxides is particularly relevant in the context of the valorization of biomass such as terpenes, [6] fatty acids [7] and sugars: [8] most of these structures contain internal olefin groups that upon epoxidation serve as useful precursors for the preparation of their bio-carbonates. Second, cyclic epoxides such as cyclohexene and cyclopentene oxide have frequently been used as suitable monomers for polycarbonate formation and their coupling with CO 2 often served to benchmark the performance of novel catalysts.…”