The use of CO as a C1 building block will be of essential importance in the future. In this context the synthesis of cyclic carbonates from epoxides and CO gained great attention recently. These products are valuable compounds in a variety of chemical fields. The development of new catalysts and catalytic systems for this atom-economic, scalable, and industrially relevant reaction is a highly active research field. Over the past 17 years great advances have been made in this area of research. This chapter covers the survey of the important known classes of homogeneous catalysts for the addition of CO to epoxides. Besides pioneering work, recent developments and procedures that allow this transformation under mild reaction conditions (reaction temperatures of ≤100 °C and/or CO pressures of 0.1 MPa) are especially emphasized.

Numerous bifunctional organocatalysts were synthesized and tested for the atom-efficient addition of carbon dioxide and epoxides to produce cyclic carbonates. These catalysts are based on phosphonium salts containing an alcohol moiety in the side chain for substrate activation through hydrogen bonding. In the model reaction, converting 1,2-butylene oxide with CO2 , 19 catalysts were tested to determine structure-activity relationships. In total, 28 epoxides were converted with CO2 to give the respective cyclic carbonates in yields of up to 99%. Even at 45 °C, the most active catalyst was able to produce cyclic carbonates selectively in high yields. The carbonates were generally obtained as analytically pure products after simple filtration over silica gel. This single-component catalyst system works under neat and mild reaction conditions and tolerates several useful moieties.

Bifunctional phosphorus-based organocatalysts proved to be highly efficient for the atom-economic reaction of CO and epoxidized oleochemicals. Notably, those products are obtained from CO and renewable feedstocks only. Structure-activity relationships have been deduced from a screening of 22 organocatalysts in a test reaction. Bifunctional catalysts based on a phosphonium salt bearing a simple phenolic moiety proved to be extraordinarily active under comparatively mild and solvent-free reaction conditions. In the presence of the most active organocatalyst 12 oleochemical carbonates were isolated in excellent yields up to 99 %. This organocatalyzed reaction represents an excellent example for the realization of the 12 Principles of Green Chemistry as well as the 12 Principles of CO Chemistry.

Taking Control! The binary catalyst system composed of MoO3 and an organic phoshponium salt [Bu4P]X proved very efficient to produce oleochemical cyclic carbonates from renewables.