- Electrophilic Mercuration Reactions of Derivatives of Deuteroporphyrin IX: New Syntheses of Coproporphyrin III, Harderoporphyrin, Isoharderoporphyrin, and S-411 Porphyrin (Dehydrocoproporphyrin)
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Treatment of copper(II) deuteroporphyrin IX dimethyl ester (17) with mercuric acetate affords a peripherally metalated species in which the 2- and 4-positions are mercurated.Acidic deuterolysis and sodium borodeuteride reduction suggest that some mercury also becomes attached to the α and β meso positions.Treatment of the dimercurated material with methyl acrylate and LiPdCl3 gives the corresponding diacrylate, 8, which can be hydrogenated to afford coproporphyrin III tetramethyl ester (7).Mercuration of copper(II) monoacetyldeuteroporphyrins IX 15 and 16 can also be readily accomplished, and in this way a new synthetic route to harderoporphyrin and isoharderoporphyrin trimethyl esters (14 and 24, respectively) is developed.A novel method for deacetylation of copper(II) porphyrins is described, and along with the mercuration/ olefin coupling reaction, this is employed in a new synthesis of the S-411 porphyrin (dehydrocoproporphyrin) obtained from meconium, as its tetramethyl ester, 34.
- Smith, Kevin M.,Langry, Kevin C.
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- Mercuration Reactions of Porphyrins: New Efficient Syntheses of Harderoporphyrin and Isoharderoporphyrin
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Treatment with mercury(II) acetate of metal complexes of porphyrins bearing peripherally unsubstituted positions gives the corresponding mercurated derivatives; using the palladium-olefin reaction, this observation is exploited in the synthesis of coproporphyrin III tetramethyl ester (2), harderoporphyrin trimethyl ester (3), and isoharderoporphyrin trimethyl ester (4).
- Smith, Kevin M.,Langry, Kevin C.
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- Identification of tetrapyrrole compounds excreted by Rhodobacter sphaeroides and sources of the methyl hydrogens of bacteriochlorophyll a biosynthesized by R. sphaeroides, based on13C-NMR spectral analysis of coproporphyrin III tetramethyl ester
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Red-fluorescent tetrapyrrole compounds excreted by Rhodobacter sphaeroides into the culture broth were concluded to be coproporphyrinogen (Copro'gen) III and uroporphyrinogen (Uro'gen) I, based on the 13C-NMR spectral identification of coproporphyrin (Copro) III tetramethyl ester and uroproporphyrin (Uro) I octamethyl ester. The sources of the methyl hydrogens of bacteriochlorophyll a were established by analysis of the 13C-NMR spectra of 2H,13C-Copro III tetramethyl ester chemically derived from 2H,13C-Copro'gen III biosynthesized through the feeding of δ-amino[2-13C]levulinic acid (ALA) to R. sphaeroides in medium containing 50% 2H2O. We confirmed the previous finding that one of the methyl hydrogens was derived from water in the medium during decarboxylation of four acetyl side chains of Uro'gen III to generate Copro'gen III. It was further shown that the other hydrogen atoms, previously reported to be derived from methylene hydrogens at C-2 of ALA, had been exchanged with hydrogen of water in the medium in the biosynthetic pathways leading from ALA to Copro'gen III.
- Iida, Katsumi,Nakamura, Masayuki,Hanamitsu, Hiroshi,Kajiwara, Masahiro
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p. 1067 - 1069
(2008/09/19)
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- Biosynthesis of Porphyrins and Related Macrocycles. Part 25. Synthesis of Analogues of Coproporphyrinogen-III and Studies of their Interaction with Copropophyrinogen-III Oxidase from Euglena gracilis
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Analogues of coproporphyrinogen-III have been synthesized in which the propionate groups respectively on ring-A and on ring-B are modified either by homologation or esterification.Coproporphyrinogen-III oxidase from Euglena gracilis acts on the analogues which possess normal substituents on ring-A to generate a vinyl group on that ring.The enzyme does not affect the analogues in which the ring-A propionate group has been changed.Conditions have been defined for the MacDonald synthesis of porphyrins which yield products of high isomeric purity.
- Robinson, John A.,McDonald, Edward,Battersby, Alan R.
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p. 1699 - 1710
(2007/10/02)
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- Biosynthesis of Porphyrins and Related Macrocycles. Part 15. Chemical and Enzymic Formation of Uroporphyrinogen Isomers from Unrearranged Aminomethylpyrromethane: Separation of Isomeric Coproporphyrin Esters
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The unrearranged pyrromethane (1) is transformed chemically mainly into uro'gen-I with a smaller amount of uro'gen-IV but only traces of uro'gen-III are formed.Uro'gen-I is produced via a tetrapyrrolic (bilane) intermediate and when the diaminase-cosynthetase enzyme system from Euglena gracilis is present, this intermediate is converted into uro'gen-III.The rearrangement step for this conversion has the same characteristics found earlier for the natural biosynthetic process from porphobilinogen.Pyrromethane (1) is not a direct biosynthetic precursor of uro'gen-III and reasons are advanced why this is understandable.Methods are developed based on high pressure liquid chromatography for the separation of all four isomeric coproporphyrin esters.
- Battersby, Alan R.,Buckley, Dennis G.,Johnson, Dawid W.,Mander, Lewis N.,McDonald, Edward,Williams, D. Clive
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p. 2779 - 2785
(2007/10/02)
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