Synthesis of Locked meso-β-Substituted Chlorins via 1,3-Dipolar Cycloaddition

A novel approach toward “locked” chlorins with increased stability has been studied in detail. The chlorin skeleton is assembled in a convergent fashion from two fragments via a porphyrin forming reaction, followed by 1,3-dipolar cycloaddition of azomethine ylides, which are formed in situ. Central to the success of the process is the presence of two electron-withdrawing groups in vicinal positions at the perimeter of the porphyrin. As a result, the 1,3-dipolar cycloaddition took place regioselectively, on the bond activated by two electron-withdrawing groups. Moreover, the chlorins formed are locked and hence more stable because of the presence of two quaternary carbon atoms. Overall, in just six steps locked chlorins were constructed from easily available materials. The large array of functionalities tolerated in this approach validates it for a broad use in more advanced studies. The correlation between the results of the 1,3-dipolar cycloaddition and dipolarophile (porphyrin) LUMO energy was extensively studied. There was a definite correlation between the reaction time and the LUMO energy level, and a partial correlation between the reaction yield and the distribution of the LUMO. Additionally, various approaches toward crucial building blocks, namely 3,4-disubstituted-2,5-diformylpyrroles, were investigated.