Recent advances in the functionalization of <i>meso</i>-triarylcorroles <i>via</i> cycloaddition reactions

Barata, Joana F. B.; Neves, Maria G. P. M. S.; Tomé, Augusto C.; Cavaleiro, José A. S.

doi:10.1142/s1088424609000668

Cited by 22 publications

(7 citation statements)

References 41 publications

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“…The postfunctionalization of corroles via cycloaddition reactions has been considered in synthetic routes aiming to obtain derivatives with specialized functionalities for various applications. Studies show that corroles, , like porphyrins, , can act as dienophiles, dienes, dipolarophiles, or 1,3-dipoles in cycloaddition reactions, although, in some cases, peculiar reactivity is observed due to unique properties of corrole. Kräutler and co-workers reported the use of the tetra(sulfoleno-fused) corrole 206 (Figure ) as a diene precursor in Diels–Alder reaction with C 60 .…”

Section: Post-functionalization Of Corrolesmentioning

confidence: 99%

Strategies for Corrole Functionalization

et al. 2016

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This review covers the functionalization reactions of meso-arylcorroles, both at the inner core, as well as the peripheral positions of the macrocycle. Experimental details for the synthesis of all known metallocorrole types and for the N-alkylation reactions are presented. Key peripheral functionalization reactions such as halogenation, formylation, carboxylation, nitration, sulfonation, and others are discussed in detail, particularly the nucleophilic aromatic substitution and the participation of corroles in cycloaddition reactions as 2π or 4π components (covering Diels-Alder and 1,3-dipolar cycloadditions). Other functionalizations of corroles include a large diversity of reactions, namely Wittig reactions, reactions with methylene active compounds, formation of amines, amides, and imines, and metal catalyzed reactions. At the final section, the reactions involving oxidation and ring expansion of the corrole macrocycle are described comprehensively.

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Section: Post-functionalization Of Corrolesmentioning

confidence: 99%

Strategies for Corrole Functionalization

et al. 2016

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“…Also, according to SciFinder, more than 70 reviews on selected aspects of corroles have been published over the last 2 decades, − although most of these publications would more accurately be classified as minireviews on very narrowly focused aspects of corrole chemistry or properties. Some of the above SciFinder-listed reviews on corroles have included discussions of the compound’s redox reactivity, − but none has been devoted exclusively to the electrochemical properties of corroles as a function of changes in the central metal ion, compound structure, or solution conditions.…”

Section: Introductionmentioning

confidence: 99%

Electrochemistry of Corroles in Nonaqueous Media

2016

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This review describes the known electrochemistry of corroles in nonaqueous media from 1980 until the present. The outline of the review is grouped according to the periodic table, proceeding from left to right, describing first monomeric free-base derivatives and then transition-metal compounds, followed by main-group corroles, before ending with a brief description of lanthanide and actinide corroles. Many similarities exist between the redox properties of metallocorroles and metalloporphyrins, but there are also many differences due, in part, to the different charges of the two conjugated macrocycles and the noninnocence of the corrole ligand in a variety of compounds. One part of this review will focus on describing redox behavior as a function of metal ion and axial ligands, while another will focus on how changes in structure of the macrocycle are associated with changes in redox behavior. It is hoped that this review will answer the majority of the readers' questions as to what has been electrochemically observed for corroles in the past while at the same time enabling the reader to utilize data in the literature to predict and "tune" what might be observed in future electrochemical studies of corroles that have yet to be synthesized and characterized.

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“…The quite original chemistry shown by the corroles has led to the first seminal exploitations of corroles in different fields 6 and for this reason the modulation of corrole properties by synthetic manipulations has become an attractive task for many researchers. However, only a few examples of corrole functionalizations have so far been reported in the literature, 7 this fact being due in part to the inherent lower stability of corroles compared with porphyrins.…”

Section: Introductionmentioning

confidence: 99%

Amination Reaction on Copper and Germanium β-Nitrocorrolates

et al. 2011

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Copper and germanium complexes of β-substituted nitrocorroles were reacted with 4-amino-4H-1,2,4-triazole to give the corresponding β-amino-β-nitro derivatives, in moderate to good yields. This is the first successful example of a vicarious nucleophilic substitution performed on corrole derivatives, because the same reaction carried out on silver complexes afforded the corresponding 6-azahemiporphycenes by way of corrole ring expansion. The first step of this work is related to the modification of a synthetic protocol for preparation of the β-substituted nitro corroles. The nitration reaction was carried out on a copper corrole using NaNO2 as the primary source of NO2− coupled with AgNO2 used as oxidant. By variation of the molar ratio of the reagents it was possible to direct the product distribution towards mono- and di-nitro derivatives. The reaction between mono- and di-nitro derivatives of (TtBuCorrCu) with 4-amino-4H-1,2,4-triazole gave good results, leading to the isolation of 2,3-(NH2)(NO2)-TtBuCorrCu and 2,18-(NH2)2-3,17-(NO2)2-TtBuCorrCu in moderate yields. To elucidate factors that influence the reaction, and to highlight the different behavior observed for different metal complex substrates, the electrochemistry of three copper complexes, TtBuPCorrCu, (NO2)TtBuPCorrCu and (NO2)2TtBuPCorrCu, were studied by cyclic voltammetry and thin-layer UV-visible spectroelectrochemistry. The nitro groups on (NO2)xTtBuPCorrCu are highly electron-withdrawing, which leads not only to a substantial positive shift of all redox potentials, but also to a unique redox behavior and UV-vis spectrum of the singly reduced product as compared to the parent compound, TtBuPCorrCu. Finally, the amination reaction was carried out on a Ge(IV) nitrocorrolate, giving in good yield the 2-amino-3-nitroderivative, which was structurally characterized by single crystal X-ray crystallography.

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Recent advances in the functionalization of meso-triarylcorroles via cycloaddition reactions

Cited by 22 publications

References 41 publications

Strategies for Corrole Functionalization

Strategies for Corrole Functionalization

Electrochemistry of Corroles in Nonaqueous Media

Amination Reaction on Copper and Germanium β-Nitrocorrolates

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