A Triple-Catalytic, Fully Biogenic Synthesis of Cyclic Carbonates

Organic carbonates play a central role as functional platform molecules for the manufacture of materials and chemicals. The atom-economical formation of cyclic carbonates from epoxides and CO₂ under mild catalytic conditions is a prime example of the concept of green chemistry. However, the sustainability of such strategies is often limited by the unfavorable parameters of the epoxide formation from olefin oxidation. Herein, a new, highly sustainable, triple-catalytic approach to the formation of biogenic cyclic carbonates from all-natural building blocks is documented. Three biogenic resources (fatty acid derivatives, O₂, CO₂) are combined with 100% atom-economy in the presence of easily accessible catalysts (porphyrin, VO(acac)₂, pyridine). Key step is a photo-oxygenation with full incorporation of O₂ into hydrocarbons. Use of the resultant cyclic carbonates in the synthesis of environmentally benign non-isocyanate polyurethanes is demonstrated.