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

ABSTRACT: Here we present a divergent synthesis of brand-new types of meso-N/O-heteroarene-fused (quinoidal) porphyrins through Rh-catalyzed β-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

SUBMITTER: Li C 

PROVIDER: S-EPMC6686728 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature