Oxidative C–N fusion of pyridinyl-substituted porphyrins

Berthelot, Mathieu; Hoffmann, G. W.; Bousfiha, Asmae; Echaubard, Julie; Roger, Julien; Cattey, Hélène; Romieu, Anthony; Lucas, Dominique; Fleurat‐Lessard, Paul; Devillers, Charles H.

doi:10.1039/c8cc01375f

Cited by 21 publications

(29 citation statements)

References 36 publications

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“…We next examined reactions involving sulfur‐centered nucleophiles that ranged from typical thiolates, which have been reported by other groups,,, to a sulfinate and a thiocyanate. The reaction of 1(2H) with 4‐chlorobenzenethiol ( 8 a ) afforded the desired meso ‐arylsufanylporphyrin 9 a(2H) in 95% yield (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…The simple treatment of a meso ‐mono‐ or di‐bromodiarylporphyrin with sodium azide in DMF under mild conditions afforded the corresponding meso ‐azidoporphyrin in good yields. Thereafter, we and other groups, reported the S N Ar reactions of meso ‐bromo‐ or nitro‐porphyrins with a variety of other nucleophiles. Most of these groups reported the use of fully meso‐ substituted porphyrins (e. g., meso ‐bromo‐ or nitro‐triarylporphyrins), most likely in order to prevent undesired substitution reactions at the unsubstituted meso ‐positions, especially when hard nucleophiles, such as oxygen‐centered anions, were used ,…”

Section: Introductionmentioning

confidence: 99%

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Versatile and Catalyst‐Free Methods for the Introduction of Group‐16 Elements at the meso‐Positions of Diarylporphyrins

et al. 2018

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This report describes versatile and catalyst-free methods for the introduction of group-16 elements at the meso-positions of diarylporphyrins. The methods involve nucleophilic aromatic substitution (S N Ar) of the meso-bromodiarylporphyrin. The reaction proceeds in almost quantitative yield in most cases. Reactions with various phenols afford the corresponding meso-phenoxyporphyrins, except for the reaction with 4-hydroxypyridine, which affords a meso-(N-pyridonyl)porphyrin. With the exception of thiocyanate, reac-tions involving sulfur-centered nucleophiles proceed smoothly and afford the corresponding functionalized porphyrins, including a meso-sulfonylporphyrin that was obtained from benzenesulfinate. To overcome problems associated with the handling of chalcogenols (instability, bad odors), we also used dichalcogenides as nucleophile precursors to afford the corresponding meso-sulfanyl or selanylporphyrins. The instability of a novel meso-tellanylporphyrin is also revealed.[a] Dr.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Versatile and Catalyst‐Free Methods for the Introduction of Group‐16 Elements at the meso‐Positions of Diarylporphyrins

et al. 2018

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“…In the general mechanism describing the reaction between a triaryl-porphyrin radical cation and a nucleophile (Scheme 3) [9], the clear advantage of electrochemical methods over chemical oxidation [10] is the precise control of the oxidation potential applied for the first oxidation, which enables avoidance of the formation of a dicationic species that can evolve erratically. In the case of polymerization, part of the efficiency of the electro-synthetic approach lies in the absence of a purification step for the polymer that is stuck to the electrode.…”

Section: Resultsmentioning

confidence: 99%

Case studies of the radical cation reactivity in meso-aryl and octaethyl porphyrins

Lamare

Ruppert

Weiss

2020

J. Porphyrins Phthalocyanines

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The reactivity of porphyrin radical cationic species derived from octaethyl porphyrin (OEP) or meso-aryl porphyrins with nucleophiles, envisioned as an access route to elaborate porphyrin dimers, has been studied and optimized in the case of OEP. Standardized conditions have been applied to various spacers to show that the success of the reaction is mostly nucleophile dependent and that the method has little chances to yield non-linear bis-porphyrins.

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“…was performed in order to maximize the formation of the monobrominated porphyrin (5). [13,14] However, despite these precautions, a mixture of FB 1, mono (5) and dibrominated (4) products was systematically obtained. Because 5 could not be isolated from FB 1 and 4, the subsequent Suzuki cross-coupling reaction was directly performed with this mixture and 8-quinolineboronic acid pinacol ester in a 50:50 mixture of dimethylformamide (DMF) and toluene in the presence of cesium carbonate as base.…”

Section: Synthesis Of Porphyrin-based Receptorsmentioning

confidence: 99%

Synthesis and Characterization of Novel Quinolyl Porphyrins as Receptors. Study of their Association with Halophenols and 4‐Nitrophenol as a Reference

et al. 2020

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In this work, new receptors built on the porphyrin scaffold were synthesized for halophenols recognition. A quinolyl group was introduced on the porphyrin's periphery as binding site, to form two series of molecules based on two distinct porphyrin frames and which were obtained in free base and zinc forms. The binding between these porphyrin‐based receptors and halophenols (2,3,4,6‐tetrachlorophenol, 2,4,6‐trichlorophenol or 2,4,6‐tribromophenol) was studied. As established by 1H NMR spectroscopy, the binding constants are in the range of two‐digit numbers, which value is correlated with the porphyrin structure (substitutive pattern, form of the free base or ZnII complex) and the pKa of the respective phenol. These data, supplemented by a X‐ray structure of one adduct complex, indicate a single interaction between the phenolic proton and the nitrogen of the quinolyl group. The binding with p‐nitrophenol was tested for comparison. The association constant increases at a scale of one order of magnitude. This net stabilization of the adduct complex in this case is explained by additional hydrogen bonds implying the nitro function, as also witnessed by X‐ray diffractometry.

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Oxidative C–N fusion of pyridinyl-substituted porphyrins

Cited by 21 publications

References 36 publications

Versatile and Catalyst‐Free Methods for the Introduction of Group‐16 Elements at the meso‐Positions of Diarylporphyrins

Versatile and Catalyst‐Free Methods for the Introduction of Group‐16 Elements at the meso‐Positions of Diarylporphyrins

Case studies of the radical cation reactivity in meso-aryl and octaethyl porphyrins

Synthesis and Characterization of Novel Quinolyl Porphyrins as Receptors. Study of their Association with Halophenols and 4‐Nitrophenol as a Reference

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