One-Pot Approach to Chlorins, Isobacteriochlorins, Bacteriochlorins, and Pyrrocorphins

Peters, Morten K; Röhricht, Fynn; Näther, Christian; Herges, Rainer

doi:10.1021/acs.orglett.8b03433

Cited by 17 publications

(30 citation statements)

References 30 publications

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“…5,10,15,20-tetraphenylporphyrin iron(III) chloride, [(TPP)Fe III Cl], and 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin, H 2 (TMPP) were purchased from commercial sources. The syntheses of H 2 (F 20 TPP), H 2 (F 20 TPP)- d 8 , and 1,3-dimethylindole were carried out according to previously published methods. Metalation of the porphyrinates to generate [(TMPP)Fe III Cl], [(F 20 TPP)Fe III Cl], and [(F 20 TPP- d 8 )Fe III Cl] and the subsequent reduction to [(THF) 2 (Por)Fe II ] complexes were carried out by following previously reported procedures .…”

Section: Methodsmentioning

confidence: 99%

Modeling Tryptophan/Indoleamine 2,3-Dioxygenase with Heme Superoxide Mimics: Is Ferryl the Key Intermediate?

Mondal

Wijeratne

2019

J. Am. Chem. Soc.

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Tryptophan oxidation in biology has been recently implicated in a vast array of paramount pathogenic conditions in humans, including multiple sclerosis, rheumatoid arthritis, type-I diabetes, and cancer. This 2,3dioxygenative cleavage of the indole ring of tryptophan with dioxygen is mediated by two heme enzymes, tryptophan 2,3-dioxygenase (TDO) and indoleamine 2,3-dioxygenase (IDO), during its conversion to Nformylkynurenine in the first and rate-limiting step of kynurenine pathway. Despite the pivotal significance of this enzymatic transformation, a vivid viewpoint of the precise mechanistic events is far from complete. A heme superoxide adduct is thought to be the active oxidant in both TDO and IDO, which, following O−O bond cleavage, presumably generates a key ferryl (Fe IV =O) reaction intermediate. This study, for the first time in model chemistry, demonstrates the potential of synthetic heme superoxide adducts to mimic the bioinorganic chemistry of indole dioxygenation by TDO and IDO, challenging the widely accepted categorization of these metal adducts as weak oxidants. Herein, an electronically divergent series of ferric heme superoxo oxidants mediates the facile conversion of an array of indole substrates into their corresponding 2,3-dioxygenated products, while shedding light on an unequivocally occurring, putative ferryl intermediate. The oxygenated indole products have been isolated in ∼31% yield, and characterized by LC-MS, 1 H and 13 C NMR, and FT-IR methodologies, as well as by 18 O 2(g) labeling experiments. Distinctly, the most electron-deficient superoxo adduct is observed to react the fastest, specifically with the most electron-rich indole substrate, underscoring the cruciality of electrophilicity of the heme superoxide moiety in facilitating the initial indole activation step. Comprehensive understanding of such mechanistic subtleties will benefit future attempts in the rational design of salient therapeutic agents, including next generation anticancer drug targets with amplified effectivity.

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Section: Methodsmentioning

confidence: 99%

Modeling Tryptophan/Indoleamine 2,3-Dioxygenase with Heme Superoxide Mimics: Is Ferryl the Key Intermediate?

Mondal

Wijeratne

2019

J. Am. Chem. Soc.

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“…Herges et al 29 have applied this synthetic procedure for the synthesis of chlorins, bacteriochlorins and isobacteriochlorins. Isobenzofuran (IBF) was used as the diene and meso-tetraphenylporphyrin (TPP) 5, mesotetrakis(pentafluorophenyl)porphyrin 9, and their Ni(II) complexes, as the dienophiles.…”

Section: Porphyrins As Dienophilesmentioning

confidence: 99%

“…The compounds were also found to be photostable under experimental conditions and both 26 and 27 showed a notable capacity to inhibit head and neck squamous carcinoma xenograft tumor model in mice under standard light conditions. 26) and of the corresponding chlorin (27), isobacteriochlorin (28) and bacteriochlorin (29) functionalized with thioglycosyl units.…”

Section: Reaction Of Porphyrins With Azomethine Ylidesmentioning

confidence: 99%

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Synthesis of chlorins and bacteriochlorins from cycloaddition reactions with porphyrins

Cavaleiro¹,

Moura²,

Monteiro³

et al. 2022

Arkivoc

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“…Porphyrins have a wide range of applications. For example, they are useful in photodynamic therapy (PDT) (Ethirajan et al, 2011;Bonnett, 1995;Peters et al, 2018a), as powerful catalysts in reduction processes in nature and in technologically important reactions (Li & Zamble, 2009;Gosden et al, 1978), or as responsive contrast agents in functional magnetic resonance imaging (fMRI) (Venkataramani et al, 2011;Dommaschk et al, 2015;Peters et al, 2018b).…”

Section: Chemical Contextmentioning

confidence: 99%

Crystal structure of a polymorph of μ-oxido-bis[(5,10,15,20-tetraphenylporphyrinato)iron(III)]

2019

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The title compound, [Fe2(C44H28N4O)2O], was obtained as a by-product during the synthesis of FeIII tetraphenylporphyrin perchlorate. It crystallizes as a new polymorphic modification in addition to the orthorhombic form previously reported [Hoffman et al. (1972). J. Am. Chem. Soc. 94, 3620–3626; Swepston & Ibers (1985) Acta Cryst. C41, 671–673; Kooijmann et al. (2007). Private Communication (refcode 667666). CCDC, Cambridge, England]. In its crystal structure, the two crystallographically independent FeIII cations are coordinated in a square-planar environment by the four N atoms of a tetraphenylporphyrin ligand. The FeIII-tetraphenylporphyrine units are linked by a μ2-oxido ligand into a dimer with an Fe—O—Fe angle close to linearity. The final coordination sphere for each FeIII atom is square-pyramidal with the μ2-oxido ligand in the apical position. The crystal under investigation consisted of two domains in a ratio of 0.691 (3): 0.309 (3).

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One-Pot Approach to Chlorins, Isobacteriochlorins, Bacteriochlorins, and Pyrrocorphins

Cited by 17 publications

References 30 publications

Modeling Tryptophan/Indoleamine 2,3-Dioxygenase with Heme Superoxide Mimics: Is Ferryl the Key Intermediate?

Modeling Tryptophan/Indoleamine 2,3-Dioxygenase with Heme Superoxide Mimics: Is Ferryl the Key Intermediate?

Synthesis of chlorins and bacteriochlorins from cycloaddition reactions with porphyrins

Crystal structure of a polymorph of μ-oxido-bis[(5,10,15,20-tetraphenylporphyrinato)iron(III)]

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