Synthesis and Functionalization of meso-Aryl-Substituted Corroles

Abstract

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.

Laser Flash Photolysis Generation and Kinetic Studies of Corrole–Manganese(v)‐Oxo Intermediates

“…All reactive substrates for LFP kinetic studies and catalytic competitive oxidations were the best available purity (Aldrich) and were passed through a dry column of active alumina (Grade I) before use. Corrole ligands employed in this study, H 3 TPFC, [3] H 3 TPC, [13] and H 3 BPMFC, [14] were prepared according to the literature procedures, and their characterization data ( 1 H NMR, UV/Vis and HRMS-ESI) were consistent with reported values.…”

“…The 5,15-bis(pentafluorophenyl)-10-(p-methoxyphenyl)corrole system (b) is abbreviated (H 3 BPFMC). Each of the corrole ligands was known, [3,13,14] as were the manganese(iii) complexes 1 a [5] and 1 c, [15] but the manganese derivative 1 b is new.…”

Cellular uptake and anticancer activity of carboxylated gallium corroles

“…Corroles have received a great deal of attention in recent years (10)(11)(12)(13), owing to dramatic advances in methods for their preparation (14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30)(31). Of interest here is a gallium(III) complex, 1 [Ga(tpfc)] (32)(33)(34)(35), where tpfc represents the trianion of 5,10,15-tris(pentafluorophenyl)corrole [H 3 (tpfc)].…”

A Perspective of One‐Pot Pyrrole–Aldehyde Condensations as Versatile Self‐Assembly Processes

“…[83,84] As early as 1996, Rose et al [85] reported the isolation of meso-tris(4-tert-butyl-2,6-dinitrophenyl)corrole as a minor by-product of a classical porphyrin synthesis, but the significance of this finding went almost unnoticed. The situation changed in 1999 with reports by Gross et al [86,87] and Paolesse et al [88,89] of one-pot corrole syntheses-initially still serendipitous-involving pyrrole-aldehyde condensations.…”