Synthesis of Porphyrinquinone and Doubly‐Fused Diporphyrin Quinone Through Oxidation of Diarylporphyrins Using a Hypervalent Iodine Compound

Treatment of a meso‐diarylporphyrin with PhI(OAc)2 in the presence of BF3 ⋅ OEt2 and propionic acid affords the corresponding porphyrinquinone in a high yield (91%). A novel quinone derived from meso‐meso β–β doubly‐fused diporphyrin was obtained as the sole byproduct (16% yield), which exhibits strong panchromatic absorption between 300 and 1000 nm. It has a low HOMO‐LUMO gap owing to expanded and low‐symmetry π‐planes. Treatment of meso‐diarylporphyrin with PhI(OAc)2 in the presence of BF3 ⋅ OEt2 and propionic acid affords the corresponding quinone in high yield. A novel quinone derived from meso‐meso β–β doubly‐linked diporphyrin is obtained as the sole byproduct. It exhibits strong panchromatic absorption between 300–1000 nm and has a narrow HOMO‐LUMO gap.