Bilitrienones from the chemical oxidation of dodecasubstituted porphyrins

Ongayi, Owendi; Vicente, M. Graça H.; Ghosh, Brahma; Fronczek, Frank R.

doi:10.1016/j.tet.2009.10.098

Cited by 12 publications

(6 citation statements)

References 42 publications

(38 reference statements)

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“…Open-chain oxygenated tetrapyrroles are obtained under several conditions, including O 2 in the presence of ascorbic acid or hydrazine (the so-called coupled oxidation of iron porphyrins) [293, 294], using thallium(III) or cerium(IV) trifluoroacetate salts [232, 295], N 2 O 4 or sodium nitrate and trifluoroacetic acid [296, 297], hydrogen peroxide [298], or meta -chloroperoxybenzoic acid (mCPBA) in pyridine [299], by reactions of metalloporphyrin π-cation radicals with nucleophiles [236], or from photo-oxidation by singlet oxygen, in the presence of light and molecular oxygen to give bilitrienones [300-308]. Porphyrins can also be reduced to dihydro- (chlorins, phlorins, porphodimethenes), tetrahydro- (isobacteriochlorins, bacteriochlorins, porphomethenes), and hexahydro-porphyrins (porphyrinogens).…”

Section: Porphyrin Functionalizationmentioning

confidence: 99%

Syntheses and Functionalizations of Porphyrin Macrocycles

Vicente¹,

Smith²

2014

COS

108

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Porphyrin macrocycles have been the subject of intense study in the last century because they are widely distributed in nature, usually as metal complexes of either iron or magnesium. As such, they serve as the prosthetic groups in a wide variety of primary metabolites, such as hemoglobins, myoglobins, cytochromes, catalases, peroxidases, chlorophylls, and bacteriochlorophylls; these compounds have multiple applications in materials science, biology and medicine. This article describes current methodology for preparation of simple, symmetrical model porphyrins, as well as more complex protocols for preparation of unsymmetrically substituted porphyrin macrocycles similar to those found in nature. The basic chemical reactivity of porphyrins and metalloporphyrin is also described, including electrophilic and nucleophilic reactions, oxidations, reductions, and metal-mediated cross-coupling reactions. Using the synthetic approaches and reactivity profiles presented, eventually almost any substituted porphyrin system can be prepared for applications in a variety of areas, including in catalysis, electron transport, model biological systems and therapeutics.

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Section: Porphyrin Functionalizationmentioning

confidence: 99%

Syntheses and Functionalizations of Porphyrin Macrocycles

Vicente¹,

Smith²

2014

COS

108

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“…In recent years, the "coupled oxidation" of metal porphyrins has proven to be quite versatile, with the scope being extended to dodeca-substituted products, as well as a variety of different oxidants. [50][51][52] Photooxidative cleavage of the TPP ring (Scheme 8) becomes possible if the central metal is either magnesium, Scheme 7. Coupled oxidation of tetraphenylporphyrinato iron(lll) chloride to give triphenylbilindione (H 3 TPBD) and tetraphenylbilatrienone (H 2 TPBT) which can be metalated with Ni, Cu and Zn.…”

Section: From Metalloporphyrinsmentioning

confidence: 99%

Making and Breaking Helical Open‐Chain Oligopyrroles

Urban,

De Feyter

2024

ChemPlusChem

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Closed‐chain oligopyrroles such as porphyrins or corroles have been well‐established in literature and experience a steadily strong interest by several fields of science. However, their open‐chain derivatives are comparatively underrepresented, despite their intriguing properties and promising applications. Here, we aim to review typical synthetic routes, as well as point towards several emergent properties, marking them as interesting candidates for various fields of study. The review focuses on two traditional methods (each starting from highly symmetric metalloporphyrins) and then expands its scope towards more recent variations before moving on to more exotic and recent highlights that have yet to be included into the canon. Key chemical reactivities (ring closure, substitution and fragmentation) are then followed by notable physicochemical properties, placing special emphasis on potential uses in molecular electronics and sensors.

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“…For each porphyrin ligand, five different divalent metals were examined, namely, Ni, 13,14,16,35,36,38,39,42,43,45,46 Cu, 33,38,40,42,44 Zn, 13,34,37,41 Pd, and Pt. 16,47 For each metalloporphyrin, the ruffled and saddled conformations were optimized.…”

Section: ■ Introductionmentioning

confidence: 99%

Energetics of Saddling versus Ruffling in Metalloporphyrins: Unusual Ruffled Dodecasubstituted Porphyrins

Conradie

Ghosh

2017

ACS Omega

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Presented herein is a first major density functional theory (BP86/D3/STO-TZ2P) survey of the energetics of saddling versus ruffling for a wide range of dodecasubstituted metalloporphyrins with M = Ni, Cu, Zn, Pd, and Pt. For the majority of X 8 TPP (i.e., β-octasubstituted- meso -tetraphenylporphyrin), the calculations indicated a clear preference for the saddled conformation, consistent with a large body of experimental data. The preference for the saddled conformation relative to the ruffled conformation was found to vary from about ∼0.3–0.4 eV for Me 8 TPP derivatives up to 1 eV for I 8 TPP and (CF 3 ) 8 TPP derivatives. For X = Ph, that is, dodecaphenylporphyrins, the saddled and the ruffled conformation are almost equienergetic, with even a slight preference for the ruffled conformation in some cases. This finding provides a satisfactory explanation for the X-ray crystallographic observation of both saddled and ruffled conformations for dodecaphenylporphyrin complexes as well as for spectroscopic evidence for conformational mobility of these complexes in solution. The calculations also indicate near-equienergetic saddled and ruffled conformations for meso -tetraacetylenyltetrabenzoporphyrins, again consonant with key crystallographic findings. By and large, both the energetics and nonplanar distortions of the metalloporphyrin derivatives correlated well with the Charton and Sterimol B 1 steric parameters of the peripheral substituents.

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Bilitrienones from the chemical oxidation of dodecasubstituted porphyrins

Cited by 12 publications

References 42 publications

Syntheses and Functionalizations of Porphyrin Macrocycles

Syntheses and Functionalizations of Porphyrin Macrocycles

Making and Breaking Helical Open‐Chain Oligopyrroles

Energetics of Saddling versus Ruffling in Metalloporphyrins: Unusual Ruffled Dodecasubstituted Porphyrins

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