Rational tetraarylporphyrin syntheses: tetraarylporphyrins from the MacDonald route

Wallace, David; Leung, Sam H.; Senge, Ma­thias O.; Smith, Kevin M.

doi:10.1021/jo00077a056

Cited by 135 publications

(74 citation statements)

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“…Common impurities formed in the synthetic steps of porphyrins are porphyrinogens, dipyrromethanes, polypyrromethanes, porphodimethene and chlorins (Figure 2). [7,22,23] Pyrrole is a very weak base. The pK a value of protonated pyrrole is 0.4.…”

Section: Resultsmentioning

confidence: 99%

Facile Purification of meso-Tetra(pyridyl)porphyrins and Detection of Unreacted Porphyrin upon Metallation of meso-Tetra(aryl) porphyrins

Zakavi¹,

Mojarrad²,

Yazdely³

2012

MHC

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In this study, different basicity of the pyridyl substituents of meso-tetra(pyridyl)porphyrins and the substituents of the common impurities associated with the synthesis of the porphyrins has been utilized to improve and simplify the purification of these porphyrins. Also, diprotonation of meso-tetraarylporphyrins with weak or strong acids and the associated shifts of the Soret and Q(0,0) bands have been used for the spectrophotometric detection of trace to substantial amounts of unreacted porphyrin upon complexation of porphyrins with iron and manganese.

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Section: Resultsmentioning

confidence: 99%

Facile Purification of meso-Tetra(pyridyl)porphyrins and Detection of Unreacted Porphyrin upon Metallation of meso-Tetra(aryl) porphyrins

Zakavi¹,

Mojarrad²,

Yazdely³

2012

MHC

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“…Total syntheses are yet only possible for selected types of substituents and still suffer from acid-catalyzed scrambling, again making this a futile endeavor in practical terms. [6] However, as mentioned, a broad range of methods for the b functionalization of meso substituents are available and strategies have emerged that put unsymmetrically meso-substituted porphyrins within reach. This involves use of either transition-metal-catalyzed coupling reactions [7] or of organometallic substitution reactions [8] for the modification of the meso positions and requires step-wise introduction of individual meso substituents in a regioselective manner, [8b] for example, through a sequence A-!AB-!ABC-!ABCD-type (6) porphyrin ( Figure 1).…”

Section: Introductionmentioning

confidence: 99%

“…In many of these cases the accessible porphyrins are routinely prepared from mixed condensation reactions, often requiring laborious purification methods resulting in low yields. Thus, there is a pressing need for simple syntheses of the latter to access the full range of ABCD porphyrins (6) by meso transformations.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Mono‐ and Disubstituted Porphyrins: A‐ and 5,10‐A₂‐Type Systems

Ryppa

Senge

Hatscher

et al. 2005

Chemistry A European J

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General syntheses have been developed for meso-substituted porphyrins with one or two substituents in the 5,10-positions and no beta substituents. 5-Substituted porphyrins with only one meso substituent are easily prepared by an acid-catalyzed condensation of dipyrromethane, pyrrole-2-carbaldehyde, and an appropriate aldehyde using a "[2+1+1]" approach. Similarly, 5,10-disubstituted porphyrins are accessible by simple condensation of unsubstituted tripyrrane with pyrrole and various aldehydes using a "[3+1]" approach. The yields for these reactions are low to moderate and additional formation of either di- or monosubstituted porphyrins due to scrambling of the intermediates is observed. However, the reactions can be performed quite easily and the desired target compounds are easily removed due to large differences in solubility. A complementary and more selective synthesis involves the use of organolithium reagents for S(N)Ar reactions. Reaction of in situ generated porphyrin (porphine) with 1.1-8 equivalents of RLi gave the monosubstituted porphyrins, while reaction with 3-6 equivalents of RLi gave the 5,10-disubstituted porphyrins in yields ranging from 43 to 90 %. These hitherto almost inaccessible compounds complete the series of different homologues of A-, 5,15-A(2)-, 5,10-A(2)-, A(3)-, and A(4)-type porphyrins and allow an investigation of the gradual influence of type, number, and regiochemical arrangement of substituents on the properties of meso-substituted porphyrins. They also present important starting materials for the synthesis of ABCD porphyrins and are potential synthons for supramolecular materials requiring specific substituent orientations.

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“…Partial and total syntheses were facilitated first by the MacDonald condensation, a [2+2] condensation utilizing dipyrromethenes, dipyrroyl ketones and dipyrromethanes [138] . Condensation methods are continuously improving and almost any desired meso or β-substituted porphyrin can be prepared today [139][140][141][142] . In parallel the functionalization of porphyrins through functional group interconversions and direct substitution reactions has progressed dramatically in the past decades [140,143] .…”

Section: Porphyrin Chemistrymentioning

confidence: 99%

Chemical Synthesis and Medicinal Applications of Glycoporphyrins

Moylan¹,

Scanlan²,

Senge

2015

CMC

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Abstract:This review presents an in-depth overview of the modification of porphyrins with bioconjugates and their applications in medicine today. Porphyrin bioconjugates ranging from nucleotides to steroids are under active scrutiny. However, carbohydrates have been at the forefront of such research in recent years and offer significant potential. This is attributed to their own selectivity to lectins on the surface of cancer cells and their influence on the amphiphilicity of the porphyrin macrocycle. These characteristics and the tendency of porphyrin photosensitizers to accumulate in tumor tissues make glycoporphyrins promising candidates for use as photosensitizers. Thus, a detailed overview of the synthesis and biological evaluation of glycoporphyrins is given with a particular focus on their applications in photodynamic therapy and their future prospects as drug candidates have been reported.

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Rational tetraarylporphyrin syntheses: tetraarylporphyrins from the MacDonald route

Cited by 135 publications

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Facile Purification of meso-Tetra(pyridyl)porphyrins and Detection of Unreacted Porphyrin upon Metallation of meso-Tetra(aryl) porphyrins

Facile Purification of meso-Tetra(pyridyl)porphyrins and Detection of Unreacted Porphyrin upon Metallation of meso-Tetra(aryl) porphyrins

Synthesis of Mono‐ and Disubstituted Porphyrins: A‐ and 5,10‐A₂‐Type Systems

Chemical Synthesis and Medicinal Applications of Glycoporphyrins

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Rational tetraarylporphyrin syntheses: tetraarylporphyrins from the MacDonald route

Cited by 135 publications

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Facile Purification of meso-Tetra(pyridyl)­porphyrins and Detection of Unreacted Porphyrin upon Metallation of meso-Tetra(aryl) porphyrins

Facile Purification of meso-Tetra(pyridyl)­porphyrins and Detection of Unreacted Porphyrin upon Metallation of meso-Tetra(aryl) porphyrins

Synthesis of Mono‐ and Disubstituted Porphyrins: A‐ and 5,10‐A2‐Type Systems

Chemical Synthesis and Medicinal Applications of Glycoporphyrins

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Facile Purification of meso-Tetra(pyridyl)porphyrins and Detection of Unreacted Porphyrin upon Metallation of meso-Tetra(aryl) porphyrins

Facile Purification of meso-Tetra(pyridyl)porphyrins and Detection of Unreacted Porphyrin upon Metallation of meso-Tetra(aryl) porphyrins

Synthesis of Mono‐ and Disubstituted Porphyrins: A‐ and 5,10‐A₂‐Type Systems