Synthesis and functionalization of meso-aryl-substituted corroles.
The Rothemund condensation reaction of pyrrole and aldehydes is an extensively used route to meso-tetraarylporphyrins, but simple modifications of the reaction conditions allow the formation of different macrocycles other than the expected porphyrin. In the presence of an excess of pyrrole, this modified Rothemund approach leads to the synthesis of meso-triary-substituted corroles. This methodology allows the preparation of a wide range of substituted corroles starting from commercially available products. Higher yields have been obtained in the case of benzaldehydes bearing electron-withdrawing substituents, while the reaction fails in the presence of 2,6-disubstituted benzaldehydes. Although if not isolated, some experimental evidences indicate that the linear 5,10,15-triphenylbilane 4 is the precursor of the final corrole ring. Reaction of 5,10,15-triphenylcorrole 2 with an excess of NBS leads to the complete bromination of the macrocycle. Spectroscopic characterization seems to indicate the formation of the porphodimethene-like structure 5, where the macrocyclic aromatic conjugation is interrupted at the 10 position. Metalation of this compound with cobalt acetate and PPh3 affords the corresponding complex. The X-ray crystal structure of triphenylphosphine [2,3,7,8,12,13,17,18-octabromo-5,10,15-tris(4-nitrophenyl)corrolato]- cobalt(III) 8 confirms the ability of corrole ring to retain an almost planar conformation when fully substituted at the peripheral position.
Paolesse
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R
Dipartimento di Scienze e Tecnologie Chimiche and INFM, Università di Roma Tor Vergata, 00133 Roma, Italy. roberto.paolesse@uniroma2.it
Nardis
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S
Sagone
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Khoury
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RG
D000447:Aldehydes / Q000737:chemistry; D001547:Benzaldehydes / Q000737:chemistry; D007202:Indicators and Reagents; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D011166:Porphyrins / Q000138:chemical synthesis* / Q000737:chemistry*; D011758:Pyrroles / Q000737:chemistry; D013329:Structure-Activity Relationship
D000447:Aldehydes; D001547:Benzaldehydes; D007202:Indicators and Reagents; D011166:Porphyrins; D011758:Pyrroles