Synthesis Of Corroles Research Articles

From Formyl-Corroles to Non-Aromatic Porphyrinoids

In 1998, it would have been impossible to imagine that only 20 years later the chemistry of one of corroles would expand to create an independent field of study. The synthesis of corroles has undergone incredible changes. From multistep strategies that attracted only practitioners in the field, the procedure has been transformed into a one-pot process from commercially available reagents. The synthesis of meso-substituted corroles evolved quickly during the first seven years after Paolesse’s and Gross’s discovery [1,2]. The methodology which led to trans-A2B-corroles (i.e., corroles bearing substituents A at positions 5 and 15 and substituent B at position 10) from dipyrranes and aldehydes was discovered in 2000 and optimized several times prior to 2006, when we discovered that as long as aldehydes and dipyrranes were relatively small and/or hydrophilic, performing this reaction in a mixture of water and methanol in the presence of HCl allowed the yields to increase from 6-30% to ~55% [3,4]. The synthetic revolution made it possible to try risky ideas in diverse areas of materials chemistry and in various biology- and medicine-oriented applications. Multiple challenges still remain in the preparation of corroles.One of those challenges is the preparation of corroles possessing CHO groups. Free formyl groups can be reacted with multiple nucleophiles forming more complex and more advanced structures. At the same time CHO is the reacting group pivotal in the corrole synthesis. Attempting to solve this conundrum we recently developed the synthesis of tris(4-formylphenyl)corrole in straightforward fashion. During the realization of this project we discovered that 10-(2-formylphenyl)corrole undergoes intramolecular Friedel-Crafts reaction leading to non-aromatic, π-expanded corrole. This divalent macrocycle possess intriguing photophysical properties and has an ability to form complexes with various metals.References Gross, Z.; Galili, N.; Saltsman, I. Angew. Chem. Int. Ed. 1999, 38, 1427−1429.Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. Chem. Commun. 1999, 1307−1308.Koszarna, B.; Gryko, D. T. J. Org. Chem. 2006, 71, 3707−3717.Orłowski, R.; Gryko, D.; Gryko, D. T. Chem. Rev. 2017, 117, 3102-3137. Figure 1

Conversion of Meso-Aryl Substituted Open-Chain Pentapyrroles to Sapphyrins: Synthesis and Electrochemistry

Sapphyrin is a 22-π aromatic pentapyrrolic macrocycle containing one direct link and four bridging methine groups between five pyrrole subunits.1 This macrocycle is an early member of the group of “expanded porphyrins” and was obtained from a pentapyrrole, a byproduct in the synthesis of corroles. A series of open-chain pentapyrroles and sapphyrins with meso-tetraaryl groups were synthesized (Figure 1) and are characterized as to their electrochemistry and protonation reactions in nonaqueous media.2 The protonation-initiated conversion of pentapyrroles to sapphyrins upon oxidation was investigated and cyclic voltammetry was used to measure the redox potentials in CH2Cl2, PhCN, and/or pyridine (Py).REFERENCES1. V. J. Bauer, D. L. J. Clive, D. Dolphin, J. B. Paine, F. L. Harris, M. M. King, J. Loder, S. W. C. Wang, R. B. Woodward, J. Am. Chem. Soc. 1983, 105,6429-6436.2. W. Shan, N. Desbois, V. Blondeau-Patissier, M. L. Naitana, V. Quesneau, C. P. Gros, Y. Rousselin, W. Huang, Z. Ou, K. M. Kadish, Chem. Eur. J., 2017 , 23, 12833-12844.Figure 1 Figure 1

Corroles and Hexaphyrins: Synthesis and Application in Cancer Photodynamic Therapy.

Corroles and hexaphyrins are porphyrinoids with great potential for diverse applications. Like porphyrins, many of their applications are based on their unique capability to interact with light, i.e., based on their photophysical properties. Corroles have intense absorptions in the low-energy region of the uv-vis, while hexaphyrins have the capability to absorb light in the near-infrared (NIR) region, presenting photophysical features which are complementary to those of porphyrins. Despite the increasing interest in corroles and hexaphyrins in recent years, the full potential of both classes of compounds, regarding biological applications, has been hampered by their challenging synthesis. Herein, recent developments in the synthesis of corroles and hexaphyrins are reviewed, highlighting their potential application in photodynamic therapy.

Manganese(III) mediated synthesis of A2B Mn(III) corroles: A new general and green synthetic approach and characterization

A new general and green synthetic protocol for the synthesis of manganese(III) metallocorroles has been developed from substituted aryl aldehydes and 5-(4-nitrophenyl)dipyrromethane using manganese salt as template. This is the first report in the synthesis of corroles: the formation of direct CC bond through metal initiation. This method allows higher working concentrations than those previously reported. The new A2B manganese(III) metallocorroles were synthesized in good yield for different applications. The single crystal X-ray structure of 10-(3,4,5-fluorophenyl)-5,15-bis(4-nitrophenyl)manganese(III) corrole is also reported and shows that manganese atom is situating atop on macrocyclic plane.

Synthesis of Corroles and Their Heteroanalogs

Corroles have come a long way from being a curiosity to being a mainstream research topic. They are now regularly synthesized in numerous research laboratories worldwide with diverse specific aims in mind. In this review we present a comprehensive description of corroles' synthesis, developed both before and after 1999. To aid the investigator in developing synthetic strategies, some of the sections culminate in tables containing comparisons of various methodologies leading to meso-substituted corroles. The remaining challenges are delineated. In the second part of this review, we also describe the syntheses of isocorroles and heteroanalogs of corroles such as triazacorroles (corrolazines), 10-heterocorroles, 21-heterocorroles, 22-heterocorroles, N-confused corroles, as well as norcorroles. The review is complemented with a short outlook.

The evolution of corrole synthesis — from simple one-pot strategies to sophisticated ABC-corroles

This review highlights synthesis procedures to obtain A3-, cis- and trans- A2B- and ABC-corroles. Synthesis methods from the early beginning of “corrole chemistry”, acid-catalyzed condensation methods of various building blocks (pyrrole, aldehyde, dipyrromethane, dipyrromethane-carbinol, and dipyrromethane-dicarbinol etc.), possible side reaction during Brønsted acid catalyzed reactions (scrambling), one-pot synthesis of corroles, and post-macrocyclization modification reactions of meso-substituted A3-corroles are discussed.

Corrole‐Decorated Porphyrin Dendrimer and Its Selective Metallation

AbstractUtilization of 4‐formylbenzaldehyde in the 2+1 approach for synthesis of corroles was regulated as to lead to either the one‐pot synthesis of meso‐meso′‐linked dimeric corrole or to a monomeric corrole with a free formyl group. The latter was used as synthon for the preparation of a dendritic porphyrin with four corroles. The different chelating properties of the similar macrocycles allow for selective insertion of zinc(II) into the central porphyrin and cobalt(III) into the peripheral corroles.

Synthesis of corrole–fullerene dyads via [4 + 2] cycloaddition reaction

Corrole–fullerene dyads were prepared by treating anthracene-functionalized corroles with fullerene. Photo physical study indicated that the excited corrole unit was quenched due to the introduction of fullerene.

ChemInform Abstract: Efficient Synthesis of 5,10,15‐Triarylcorroles Using Amberlyst 15 under Solvent‐Free Conditions.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Efficient synthesis of 5,10,15‐triarylcorroles using amberlyst 15 under solvent‐free conditions

Abstractmagnified imageAn efficient and convenient synthesis of 5,10,15‐triarylcorroles by the condensation of aryl aldehydes with pyrrole catalyzed by Amberlyst 15 followed by oxidative cyclization with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) at room temperature has been reported. Amberlyst 15 is more efficient catalyst under solvent free conditions and DDQ is more suitable oxidant in dichloromethane than those of other catalysts and oxidants, respectively, for the synthesis of corroles at room temperature.

Efficient synthesis of aryldipyrromethanes in water and their application in the synthesis of corroles and dipyrromethenes

In this paper, we describe the efficient and selective synthesis of aryldipyrromethanes in aqueous medium by acid-catalyzed (HCl) condensations of aromatic aldehydes with 3 equivalents of pyrrole at room temperature. The precipitated aryldipyrromethanes can be isolated directly from the reaction mixture in an essentially pure state by simple filtration. Time control seems to be essential to avoid significant formation of the tripyrromethane analogue and the reaction time is strongly dependent on the nature of the aromatic aldehyde. A one-pot synthesis of several aryldipyrromethenes and various novel meso-aryl-substituted trans-A2B-corroles was also achieved starting from the obtained aryldipyrromethanes. Trichloroacetic acid was the preferred acid catalyst for the preparation of meso-triarylcorroles from the condensation of 5-(2,6dichlorophenyl)dipyrromethane with more reactive aldehydes, while trifluoroacetic acid was preferred for less reactive substrates.

Synthesis and properties of a corrole with small and electron-withdrawing substitutents, 5,15-bis(trifluoromethyl)-10-pentafluorophenylcorrole

Several methodologies for the synthesis of corroles that carry minimal-sized electron-withdrawing substituents at the meso- C atoms were investigated; of these the one based on dypyrromethane/aldehyde condensation was fruitful. The new corrole with one C 6 F 5 and two CF 3 groups, as well as its cobalt(III) complex, were fully characterized by spectroscopy and X-ray crystallography.

Superoxide induced cyclizations of metallo-2,2'-bidipyrrins

The reaction of the open-chain tetrapyrrolic ligand 2,2'-bidipyrrin with molecular dioxygen in the presence of a catalytic amount of manganese(II)-acetate was found to produce 10,10'-diformyl-2,2'-bidipyrrin with a remarkable selectivity. To identify the active oxidant in this transformation, 2,2'-bidipyrrin was treated with potassium superoxide, sodium peroxide and manganese(III) acetate, respectively, in dry DMF. While superoxide produces the dialdehyde in high yield, the treatment with peroxide or manganese(III) acetate leads to decomposition only. Nickel(II)-, palladium(II)- and copper(II)-2,2'-bidipyrrin were found to undergo macrocyclization reactions when treated with potassium superoxide in dry DMF at room temperature. While the respective 10-oxocorrolates are formed from the nickel(II)- and palladium(II)-2,2'-bidipyrrins, the copper(II) chelate reacts very slowly and yields copper(III) corrole in low yield. The results strongly point to superoxide as the active oxidant in a recently found new synthesis of corroles.

Microwave-assisted synthesis of corroles

The recently developed Gross's method for the synthesis of corroles has been modified and successfully applied to the preparation of new free base tris-aryl- and tris-pyrimidyl-corroles using solvent-free conditions and microwave irradiation. Compared to conventional heating, the microwave technique afforded an increase in corrole yields of ca. 30% and led to noticeably cleaner reaction mixtures. It is demonstrated that short reaction times and high temperatures are required to afford optimum yields.

Synthesis of corroles bearing up to three different meso substituents.

[reaction: see text] We have developed a new method that affords regioisomerically pure corroles possessing up to three different substituents at the meso positions. The corrole formation reaction involves the acid-catalyzed condensation of a dipyrromethane-dicarbinol with pyrrole followed by oxidation with DDQ. ABC-Type corroles were synthesized for the first time according to this procedure.

ChemInform Abstract: Recent Advances in the Synthesis of Corroles and Core‐Modified Corroles

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Recent Advances in the Synthesis of Corroles and Core-Modified Corroles

The aim of this review is to highlight recent progress in the synthetic methodologies leading to corroles and core-modified corroles. Emphasis is put on corroles with meso substituents. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

ChemInform Abstract: Manganese as a Template: A New Synthesis of Corrole.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Sterically encumbered triarylcorroles from aryldipyrromethanes and aromatic aldehydes

A two-step synthesis of corroles from dipyrromethanes and aromatic aldehydes has been achieved. Acid-catalyzed [2+2] condensation of (2,6-dichlorophenyl)dipyrromethane with electron deficient aldehydes in CH 2Cl 2 followed by cyclization and oxidation in propionitrile or CH 2Cl 2, in the presence of DDQ or chloranil gave corroles in good yields.

Manganese as a template: a new synthesis of corrole.

The reaction of 2,2'-bisdipyrrins 1, 2, and 3 with manganese(II) acetate tetrahydrate and molecular dioxygen yields the manganese(III)corroles 4, 5 and 6, which are readily demetalated to the respective free-base corroles.