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In the present paper, we report the synthesis of free 5‐ and 10‐monophenylcorroles, 4 and 3 respectively as well as the first example of molecular oxygen oxidation of the corrole macrocycle identified as an open chain tetrapyrrole (biliverdin) structure 7. Reaction of 1 and 2 in acetic acid leads to a mixture of two a,c‐biladienes 3b and 4b and therefore to a mixture of two corrole isomers 3 and 4. Reaction of 1 and 2 in trifluoroacetic acid leads only to the symmetrical corrole isomer 3 in 41% yield.

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A smooth and convenient one-step synthesis of 3,4disubstituted pyrrole-2,5-dicarbaldehydes 2 is reported. This reaction involves the condensation of b-substituted pyrrole-2-carboxylic acids with triethyl orthoformate in trifluoroacetic acid to give the title compounds in good yield.

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