Despite of the many similarities between corroles and porphyrins, the chemistry of the former remained undeveloped for decades because of severe synthetic obstacles. The recent discoveries of facile methodologies for the synthesis of triarylcorroles and the corresponding metal complexes allowed for their utilization in various fields. This survey reveals many examples where corroles were used as the key components in catalysis, sensing of gaseous molecules and medicine-oriented research. The focus in all these cases was on the special features of corroles: stabilization of high valent transition metal ions, unique photophysical properties, large NH acidity, facile synthetic manipulation and distinct catalytic properties. The latter aspect includes several examples of reactions that are not catalyzed by any non-corrole metal complex, such as the iron-based aziridination by Chloramine-T, the clean disproportionation of peroxynitrite, and the very facile N-H activation of amines.

A thorough mechanistic investigation has been performed on the reactions of primary and secondary amines with diazoacetates, which proceed uniquely quickly and efficiently when catalyzed by iron(III) corroles and porphyrins. Two major differences in relation to other metal-based catalysts are that the iron complexes are not poisoned by excess amine and that metal-carbene intermediates are apparently not involved in the reaction pathway. The results instead point towards nitrogen ylide intermediates formed by nucleophilic attack of the amines on diazoacetate-coordinated iron complexes. Nitrogen ylides are also formed when allyl- and propargyl-substituted tertiary amines react with diazoacetates, a scenario that smoothly leads to 2,3-rearrangement reaction products with catalytic amounts of the iron(III) complexes. Similar findings regarding the superiority of the iron(III) complexes (in terms of catalyst loading, chemical yields, and reaction conditions) were obtained with thiols (S--H insertion) and sulfides (2,3-rearrangement reactions), which suggest similar mechanisms operate in these cases.

Iron complexes of porphyrins (and corroles to a lesser extent) are the first catalysts to utilize ammonia for the synthesis of N-free amino acid esters.

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Iron corroles and porphyrins catalyze the reactions of amines with ethyl diazoacetate extremely efficiently, leading to complete and rapid conversion into N-substituted glycine ethyl esters by simultaneous addition of the substrates to the catalysts. The selectivity toward activation of the NH bonds is remarkable and quite different from other catalysts.