An unusual [4 + 2] fusion strategy to forge meso-N/O-heteroarene-fused (quinoidal) porphyrins with intense near-infrared Q-bands

Here we present a divergent synthesis of brand-new types of meso-N/O-heteroarene-fused (quinoidal) porphyrins through Rh-catalyzed beta-C-H activation/annulation of 5,15-dioxoporphyrins and dioxime derivatives with alkynes, in which the synthetic disconnections are difficult to access through the commonly used intramolecular cyclization strategy. Using the O-methyl oxime as a traceless oxidizing directing group, the meso-N-embedded pyridine-fused anti-quinoidal porphyrin 3 and pyridinium-fused cation 4 are formed with controllable chemoselectivity and complete anti-selectivity. Replacing the exocyclic oxime with a carbonyl group delivers the pyran-fused porphyrin 5, achieving structural conversion from a quinoidal conformation to a stable porphyrin macrocycle. Further oxidation of the expanded dimer 5ea gives the oxonium 6, which exhibits intense near-infrared (NIR) Q-bands up to 1300 nm. Theoretical studies demonstrate that the incorporation of a heteroatom at the meso-position enables more effective pi-extension, resulting in a 22 pi aromatic (vs. 18 pi aromatic) character of pyran-fused porphyrins (syn/anti-5aa). Compared with the commercially available methylene blue (MB), syn-5al exhibits a better ability (phi(Delta) = 0.61) to sensitize singlet oxygen (O-1(2)) when irradiated with a 680 nm laser beam, and has potential as a photodynamic therapy (PDT) photosensitizer in the body's therapeutic window (650-900 nm).