Totalsynthese von [α,γ‐<sup>14</sup>C<sub>2</sub>]‐Uroporphyrin III

Franck, Burchard; Gantz, Dietrich; Hüper, Fritz

doi:10.1002/ange.19720840910

Cited by 17 publications

(3 citation statements)

References 7 publications

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“…It was confirmed by the chemical degradation of the hemin (5 a ) . The phyllopyrrole (6) formed after methylating cleavage (HI/CH,O) contained, in addition to 14C, 31 % of the 3H-radioactivity of the hemin (5 a ) and the phyllopyrrolecarboxylic acid ( 7 ) contained, in addition to 3H, 35% of the I4C-radioactivity.…”

Section: ( L O ) Double Bond I N S T E a D Of 2tmentioning

confidence: 99%

Total Synthesis of [¹⁴C]‐ and [³H]‐ Labeled Tripyrrole Precursors for Heme Biosynthesis

Franck

Fels

Ufer

et al. 1977

Angew. Chem. Int. Ed. Engl.

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As has been demonstrated for heme (2)[*1 and vitamin uroporand is probably also the case for A-&+&s NH HN ,,-f--, I I'\ Ps;. I. -- 13)---P A H2N*PS phyrinogen I11 (I) is a precursor of and key compound in the biosynthesis of biologically active porphyrins. Uroporphyrinogen I11 (I) is characterized by inversion of pyrrole nucleus D (in the dotted circle), together with its side chains. Isotopically labeled, biogenetically significant tripyrrolescS1 are of importance for the elucidation of the biosynthesis of (I) from linear, oligopyrrole precursors, as well as for elucidation of the physiologically important "pyrrole inversion". We will now report the first total syntheses of the ['"Cl-and ['HIlabeled tripyrroles (3) and ( 4 ) respectively; each of them contains a terminal, inverted pyrrole nucleus and, of all the eight possible isomeric tripyrroles, these could well be the precursors preferred for biosynthesis. On account of the complicated structure and high reactivity of the tripyrroles (3) and ( 4 ) , pathways for their syntheses were selected which, with extensive use of the convergence yielded the stable well-protected depot compounds (7) and ( 8 ) from which (3) and ( 4 ) could be liberated by easy, mild reactions. Radioisotopes with different radiation energies were used to label the two tetrapyrroles so that when they were mixed, the individual rates of incorporation [of (3) and (4)] could be directly determined by measuring the radioactivities of the biosynthetic product, heme (2). The positions of the labels were chosen so that the "C-and 3H-isotopes (a) could be introduced into (3) and (4) respectively as late as possible in the multi-step synthesis, (b) would not be lost during biogenetic conversions, and (c) could be located in heme (2) by simple degradation.The ''C-labeled reactant for the synthesis of the tripyrrole (7) The labeled tripyrroles (3) and ( 4 ) were prepared from the hydrobromides (7) and (8) respectively, with the yields specified, in four steps; these steps were conversion to the free base (NH,), hydrogenolysis of the benzyl ester (H,/Pd), decarboxylation (CF3CO2H, 0 "C), and alkaline saponification (2 N KOH, 20°C). Experimental (7): A solution of ( 5 ) (418mg, 1.08mmol; 2.5mCi) and (6) (624mg, 1.08mmol) in 25ml methanol was mixed with 47 % HBr (0.8ml) and stirred for 4 h at 20°C. After 21 days in the refrigerator (7) (664mg, 60 %) containing 1.45 mCi (58 %) had crystallized out.

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Section: ( L O ) Double Bond I N S T E a D Of 2tmentioning

confidence: 99%

Total Synthesis of [¹⁴C]‐ and [³H]‐ Labeled Tripyrrole Precursors for Heme Biosynthesis

Franck

Fels

Ufer

et al. 1977

Angew. Chem. Int. Ed. Engl.

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“…HBr versetzt und 4 h bei 20°C geriihrt. Nach 21 Tagen im Tiefkiihlschrank waren 644 mg (60%) ( 7 ) rnit 1.45 mCi (58 %) auskristallisiert.…”

Section: Arbeitsvorschriftunclassified

“…Hexafluoraceton scheint bei dieser Reaktion als Zwischenprodukt aufzutreten, durch Umsetzung nach (b) 1aDt sich die Ausbeute an ( 3 a ) auf das Doppelte steigern: CF3NO + (CF3)zCNz + (CF3)zCO ( 3 U ) (7) und (8) (3) und (4) moglichst spat eingefuhrt, b) bei biogenetischen Umwandlungen nicht abgespalten werden und c) im Ham (2) durch einfachen Abbau lokalisierbar sind.…”

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Totalsynthese [14C]- und [3H]-markierter Tripyrrol-Vorstufen der Häm-Biosynthese

et al. 1977

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Zur Biosynthese von Häm und Vitamin B₁₂ aus [α,γ‐¹⁴C₂]‐Uroporphyrinogen III

et al. 1972

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Totalsynthese von [α,γ‐¹⁴C₂]‐Uroporphyrin III

Cited by 17 publications

References 7 publications

Total Synthesis of [¹⁴C]‐ and [³H]‐ Labeled Tripyrrole Precursors for Heme Biosynthesis

Total Synthesis of [¹⁴C]‐ and [³H]‐ Labeled Tripyrrole Precursors for Heme Biosynthesis

Totalsynthese [14C]- und [3H]-markierter Tripyrrol-Vorstufen der Häm-Biosynthese

Zur Biosynthese von Häm und Vitamin B₁₂ aus [α,γ‐¹⁴C₂]‐Uroporphyrinogen III

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Totalsynthese von [α,γ‐14C2]‐Uroporphyrin III

Cited by 17 publications

References 7 publications

Total Synthesis of [14C]‐ and [3H]‐ Labeled Tripyrrole Precursors for Heme Biosynthesis

Total Synthesis of [14C]‐ and [3H]‐ Labeled Tripyrrole Precursors for Heme Biosynthesis

Totalsynthese [14C]- und [3H]-markierter Tripyrrol-Vorstufen der Häm-Biosynthese

Zur Biosynthese von Häm und Vitamin B12 aus [α,γ‐14C2]‐Uroporphyrinogen III

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Totalsynthese von [α,γ‐¹⁴C₂]‐Uroporphyrin III

Total Synthesis of [¹⁴C]‐ and [³H]‐ Labeled Tripyrrole Precursors for Heme Biosynthesis

Total Synthesis of [¹⁴C]‐ and [³H]‐ Labeled Tripyrrole Precursors for Heme Biosynthesis

Zur Biosynthese von Häm und Vitamin B₁₂ aus [α,γ‐¹⁴C₂]‐Uroporphyrinogen III