Study On The Synthesis Of Metalloporphyrins And Their Catalytic Properties In The Coupling Reaction Of CO₂ And Epoxides

Transformation of carbon dioxide is of great importance in terms of greenhouse gas, abundant and cheaper feedstocks. One of the most successful examples is the synthesis of cyclic carbonates from CO2 and epoxides. The cyclic carbonates are widely used as organic syntheses intermediates, and raw materials for plastics etc.In the thesis, achiral and chiral metalloporphyrins were synthesed and catalyzed the coupling of CO2 and epoxides.1. Tetrakis(4-carboxyphenyl)porphyrin was synthesized following the procedures of Alder. Then tetrakis(4-carboxyphenyl) porphyrinato cobalts (TCPPCo (â…¡),TCPPCo(â…¢)CF3COO,TCPPCo(â…¢)OAc,TCPPCo(â…¢)Br,TCPPCo(â…¢)Cl) were synthesized. A catalysts of tetrakis(4-carboxyphenyl) porphyrinato cobalt(III) and PTAP were developed to catalyze the coupling reaction of carbon dioxide and epoxides at room temperature. we found that TCPPCo(â…¢)CF3OO/PTAT is a novel and high efficient system in the reaction.2. A series of chiral porphyrin complexes (7,8a,8b) were synthesized in multi-steps from natural amino acids and BINOL, then applied in the asymmetric cyclicaddition reaction of carbon dioxide with epoxides. The results shown some of enantioselectivity.