Das Pyrrocorphin‐Ligandsystem: Synthese des 2,2,7,7,12,12,17‐Heptamethyl‐2,3,7,8,12,13‐hexahydroporphyrins. Kurzmitteilung

Sehwesinger, Reinhard; Waditschatka, Rudolf; Rigby, James H.; Nordmann, R.; Schweizer, W. B.; Zaß, Engelbert; Eschenmoser, Albert

doi:10.1002/hlca.19820650220

Cited by 34 publications

(6 citation statements)

References 24 publications

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“…Schema 9). Damit aber steht der Chromophortyp von F430M in unmittelbarer ((chemischer Nachbarschaft)) zum Strukturtyp der Porphyrinogene, denn letzterer ist via die kiirzlich aufgefundene Porphyrinogen F't Pyrrocorphinat-Tautomerisierung[39] [40] direkt mit dem Strukturtyp der Corphine verbunden. Diese Zusammenhange weisen darauf hin, dass die Entdeckung von Faktor F430von der offensichtlich bedeutungsvollen biologischen Wirkung ganz abgesehenauch im Hinblick auf kurzlich aufgeworfene [41], den Ursprung der natiirlichen Porphinoidstrukturen betreffende Fragen wesentliche Einsichten zu geben verspricht.…”

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Zur Kenntnis des Faktors F430 aus methanogenen Bakterien: Struktur des porphinoiden Ligandsystems

Pfaltz

Jaun

Fässler

et al. 1982

Helvetica Chimica Acta

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294

142

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A structure is proposed for F430M, a non-cristalline methanolysis product of isolates of the nickel-containing, porphinoid factor F430 from Methanobacterium thermoautotrophicum.Crucial to the structure determination are five incorporation experiments with M . thermoautotrophicum (strain Marburg) in which the specifically m~n o -~~C -l a beled biosynthetic precursors (2-13C)-, (3-I3C)-, (4-I3C)-, (5-I3C) ALA (ALA = 6-amino-levulinic acid) and ~-(methyl-'~C)methionine were incorporated into F430 with high efficiency. The I3C-NMR.-spectra of the specifically labeled F430M samples derived therefrom, together with the UV./VIS. spectral data of F430M, contain all the information necessary for the deduction of the constitution of the F430M chromophore, assuming the established pattern of porphinoid biosynthesis to be operative in F430 biosynthesis. IH-NMR. spectroscopy and, in particular, 'H-NMR.-NOE-difference spectroscopy corroborates and completes the constitutional assignments and, furthermore, makes possible an almost complete derivation of the molecule's relative configuration. Schemes 3 and 4 summarize the results of 'H-NMR. spectroscopy, presenting them within the context of the proposed structure for F430M. The assignment of absolute configuration implied in the formula is given preference because of F430M's very close structural and (assumed) biosynthetic relationship to sirohydrochlorin and vitamin BI2 (with respect to ring C, the assignment is based on degradative evidence).According to the proposed structure, the nickel complex F430M possesses an uroporphinoid (Type 111) ligand skeleton with an additional carbocyclic ring and a chromophore system not previously encountered among natural porphinoids. It can be considered to be a (tetrahydro) derivative of the corphin system, combining structural elements of both porphyrins and corrins. I ) Arbeitsgruppe f u r physikalische organische Chemie (Leitung Prof. J . F. M. Oh), Organisch-chemisches Laboratorium der ETHZ. 0018-019X/82/3/0828-38$01.00/0 0 1982 Schweizerische Chemische Gesellschaft HELVETICA CHIMICA ACTA -Vol. 65, Fasc. 3 (1982) -Nr. 81 829 14) Die Strukturen I, J und K zeigen die hier als UV./VIS.-Modellsysteme massgebenden Chromophortypen. u b e r deren UV./VIS.-Spektren vgl. (151. I J K

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unclassified

Zur Kenntnis des Faktors F430 aus methanogenen Bakterien: Struktur des porphinoiden Ligandsystems

Pfaltz

Jaun

Fässler

et al. 1982

Helvetica Chimica Acta

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294

142

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“…Thus, with several modifications, the Eschenmoser sulfide contraction/iminoester cyclization method [154] was incorporated in the assembly of the four monocyclic pyrrole precursors (11,12,14,15) to yield 19. Establishing protecting groups X at C-7 and C-13 allowed for double elimination yielding the tetrahydroporphyrin and upon oxidation gave the chromophore 21 (Scheme 3) [153] .…”

Section: Total Synthesis Of Tolyporphyinmentioning

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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“…The first C-methyl group is placed in ring A" to form an intermediate which probably has structure (24) or a doublebond tautomer of it ; this is precorrin-1 (Scheme 12). Methylation occurs next at ring B to yield precorrin-2 (25), of proven structure,20 which was demonstrated to be the true intermediate by direct isolation and by re-incorporation experiments.20 It is very probable that the trimethylated intermediate, possessing the initially surprising methyl group at C-20, is also enzymically generated and transformed at the dihydro level of oxidation, (26); this intermediate is precorrin-3.…”

Section: The Biosynthesis Of Vitamin Bmentioning

confidence: 99%

Nature's pathways to the pigments of life

Battersby¹

1987

Nat. Prod. Rep.

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This article is based on the Robert Robinson Lecture that was delivered on 10th April 1986 at the Annual Congress of The Royal Society of Chemistry, at the University of Warwick 1 Introduction 2 The Biosynthesis of Uroporphyrinogen 111 3 First Studies on the Stereochemistry of Action of 4 The Mechanism of Action of Cosynthetase 5 The Biosynthesis of Vitamin B,, 6 Acknowledgements 7 References Deaminase ' Enzyme Nomenclature 1984 ') for deaminase is porphobilinogen deaminase [E.C. 4.3.1.81 (the previous recommended name was hydroxymethylbilane synthase) and that for cosynthetase is uroporphyrinogen-111 synthase [E.C. 4.2.1.751. NPR 4 6 * The parent macrocycle which appears (in a highly substituted form) in cobyrinic acid (22) is called corrin.

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Das Pyrrocorphin‐Ligandsystem: Synthese des 2,2,7,7,12,12,17‐Heptamethyl‐2,3,7,8,12,13‐hexahydroporphyrins. Kurzmitteilung

Cited by 34 publications

References 24 publications

Zur Kenntnis des Faktors F430 aus methanogenen Bakterien: Struktur des porphinoiden Ligandsystems

Zur Kenntnis des Faktors F430 aus methanogenen Bakterien: Struktur des porphinoiden Ligandsystems

Chemical Synthesis and Medicinal Applications of Glycoporphyrins

Nature's pathways to the pigments of life

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