General and Scalable Approach to A2B‐ and A2BC‐Type Porphyrin Phosphonate Diesters

摘要: A two-step reaction sequence for accessing meso-(dialkoxyphosphoryl)porphyrins from readily available trans-A2-type porphyrins was developed. This approach involves bromination and subsequent palladium-catalyzed phosphonylation. Optimal conditions both steps were identified after exploration of various parameters such as solvent, temperature catalyst. series dialkoxyphosphoryl-substituted A2B-porphyrins Zn3(a–g) bearing electron-donating, electron-withdrawing or sterically bulky substituents at the meso-aryl groups prepared in overall yields close to 40 %. These compounds, being air-stable soluble most organic solvents, are valuable synthetic intermediates because they can be transformed into functionalized trans-A2BC-type through regioselective functionalization unsubstituted meso position macrocycle. Therefore, this offers considerable promise application synthesis porphyrins, including water-soluble derivatives, push-pull chromophores bis(porphyrin)s.