Selective Substitution of Corroles:  Nitration, Hydroformylation, and Chlorosulfonation

Abstract

This work demonstrates the feasibility and power of electrophilic substitution on the peripheral carbon atoms of triarylcorroles as a synthetic tool to new derivatives. The large difference in the reactivity of the various carbon atoms on the macrocycle was shown to be of electronic rather than steric origin. A careful choice of reagents and a delicate control of reaction conditions allowed the selective syntheses of novel derivatives, in all of which substitution took place selectively in only the directly joined pyrrole rings of the macrocycle. This was proven by a combination of X-ray crystallography of the various products and detailed analysis of their NMR spectra.

Synthesis of amphiphilic sulfonamide halogenated porphyrins: MALDI-TOFMS characterization and evaluation of 1-octanol/water partition coefficients

“…According to the literature, the aromatic electrophilic chlorosulfonation of porphyrins and corroles using chlorosulfonic acid is an attractive method to obtain the corresponding chlorosulfonic derivatives with high yields and purity. The chlorosulfonations of 5,10,15,20-tetrakisphenylporphyrin (TPP), 5,10,15,20-tetrakis(2-chlorophenyl)porphyrin (TCPP) and TDCPP proceed with excellent selectivity for the phenyl ring, as opposed to the selective substitution of b-pyrrole H atoms in corroles 23,24 yielding the stable tetra-chlorosulfonated porphyrinic compounds with high yields. 12,25,26 These chlorosulfonates revealed also excellent reactivities towards nucleophiles like water, amines, alcohols or amino acids.…”

“…12,25,26 These chlorosulfonates revealed also excellent reactivities towards nucleophiles like water, amines, alcohols or amino acids. 12,[23][24][25][26][27][28] Metallocomplexes of amphiphilic sulfonamide porphyrins proved to be quite good catalysts for epoxidation of alkenes 29 and oxidation of azo dyes in biphasic systems using hydrogen peroxide as oxidant. 30 Furthermore, the synthesis of amphiphilic corroles with sulfonic acid head groups and their multiple applications on bio-mimetic catalysis, 31,32 bio-medicine 33,34 and photovoltaic cells 35 have been recently described by Gross.…”

Cellular uptake and anticancer activity of carboxylated gallium corroles

“…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)]. 1 is highly fluorescent, with an emission quantum yield far exceeding that of its zinc porphyrin analog (36)(37)(38).…”

Modifications of Porphyrins and Hydroporphyrins for their Solubilization in Aqueous Media

“…On the other hand, sulfonation readily leads to the solubilization of porphyrins in aqueous media. Interestingly, the porphyrin is protonated during the sulfonation step and is thus protected by the dicationic charge from getting sulfonated at the β-positions along an electrophilic aromatic substitution pathway, in contrast with the regioselective β-sulfonation of the less basic corroles using chlorosulfonic acid [111][112][113].…”