A novel stereoselective synthesis of the macrocycle of haem d1 that establishes its absolute configuration as 2R,7R

Micklefield, Jason; Mackman, Richard L.; Aucken, Christopher J.; Beckmann, Marion; Block, Michael H.; Leeper, Finian J.; Battersby, Alan R.

doi:10.1039/c39930000275

Cited by 16 publications

(12 citation statements)

References 8 publications

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“…5). After precorrin-2, the last precursor common to siroheme, coenzyme F430, heme dl, and coenzyme B12 (21,26) ( Fig. 1), the pathway specifically dedicated to corrinoids is initiated by the introduction of the C-20 methyl group which is expelled later along with the C-20 bridge carbon in the form of acetic acid, as a result of the ring contraction process (2,27).…”

Section: Discussionmentioning

confidence: 99%

Biosynthesis of the corrin macrocycle of coenzyme B12 in Pseudomonas denitrificans

et al. 1993

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Studies with cell-free protein preparations from a series of recombinant strains of Pseudomonas denitrificans demonstrated that precorrin-3 is converted into a further trimethylated intermediate, named precorrin-3B, along the pathway to coenzyme B12. It was then shown that the part of the pathway from precorrin-3 (called precorrin-3A hereafter) to precorrin-6x involves three intermediates, precorrin-3B, precorrin-4, and precorrin-5. Precorrin-3B was isolated in its native (reduced) as well as its oxidized (factor-IHB) states, and precorrin-4 was isolated in its oxidized form only (factor-IV). Both factors were in vitro precursors of precorrin-6x. The synthesis of precorrin-6x from precorrin-3A was shown to be catalyzed by four enzymes, CobG, CobJ, CobM, and CobF, intervening in this order. They were purified to homogeneity. CobG, which converts precorrin-3A to precorrin-3B, was found to be an iron-sulfur protein responsible for the oxidation known to occur between precorrin-3A and precorrin-6x, and CobJ, CobM, and CobF are the C-17, C-11, and C-1 methylases, respectively. The acetate fragment is extruded after precorrin-4 formation. This study combined with our recent structural studies on factor-IV

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Section: Discussionmentioning

confidence: 99%

Biosynthesis of the corrin macrocycle of coenzyme B12 in Pseudomonas denitrificans

et al. 1993

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“…Die Griinde fur die Deformation der Ligandensysteme von Metall-porphyrinaten und -corrinaten sind von Kratky und Eschenmoser systematisch untersucht und detailliert 8,I2,) -3,7,12,17-tetramethyl-8.13-dioxo-21 H,23H-porphm-2,18-dipropanoato(2-) Eggenstein-Leopoldshafen, unter Angabe der Hinterlegungsnummer CSD-53390, der Autoren und des Zeitschriftenzitats angefordert werden.…”

Section: Stereoselektive Synthese Vonunclassified

“…(&)- (( 7 RS,12 SR,8, terrahydro-3,7,12,17-tetramethyl-2lH,23H-porphin-2,l8-dipropanoato(2-/-N2',N2z,N23,N24~nickel(II~ (rac-7b). Entsprechend der Vorschrift fur rac-5a, rnit 283 mg (0,37 mmol) rac-fib, 285 mg ( (7), 665 (6), 664 (12), 663 (12), 662 (14), 652 (13), 651 (20), 650 (30), 649 (29).…”

Section: -Dimethyl-712-bis[2-(diniethylamino)-2oxoethylmentioning

confidence: 99%

“…Die vorliegende Arbeit beschreibt ausfuhrlich unsere Ergebnisse, iiber die wir in zwei vorlaufigen Mitteilungen berichtet hatten [l]. Battersby und Mitarbeitern [8] gelang es schliesslich, durch eine ca. 35 Schritte umfassende Totalsynthese des Metall-freien Liganden von Ham d, die ') Kurzmitteilungen: [I] absolute Konfiguration zu bestimmen, da ein Glutaminsaurederivat bekannter Konfiguration als Synthesebaustein diente.…”

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Stereoselektive Synthese des Nitrit‐reduzierenden Cofaktors Häm d₁ ausgehend von Hämatoporphyrin

Romanowski

Mai

Kusch

et al. 1996

Helvetica Chimica Acta

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The nitrite-reducing cofactor heme d, has been synthesized in a few synthetic steps, starting from readily accessible hematoporphyrin dimethyl ester (rac-4a). A single-crystal structure analysis of the synthesized target molecule rac-l0a unequivocally established the constitution and the relative configuration of heme d, (3). 1. Einleitung. -Isobakteriochlorine 1, die als charakteristisches Strukturelement zwei benachbarte, partiell gesattigte Pyrrol-Ringe im Porphyrin-Grundgerust besitzen, sind in der Natur durch die Sirohydrochlorine 2a (Faktor 11) und 2b (Faktor 111), Siroham (2c) und Ham d, (3) vertreten. Die Dihydroderivate der Sirodydrochlorine 2a und 2b sind wichtige Zwischenverbindungen in der Vitamin-BIZ-Biosynthese, wahrend ihr Eisen-haltiger Vertreter Siroham (2c) als Cofaktor in Sulfit-und Nitrit-Reduktasen von Bakterien und Pflanzen eine bedeutende Rolle fur die globalen Kreislaufe von Schwefel und Stickstoff spielt [2]. Ham d, (3) ist einer von zwei Cofaktoren in Cytochrom cd,, das fur die Reduktion von Nitrit zu Distickstoffmonoxid (N,O) in chemoautotrophen Bakterien wie Pseudomonus aeruginosa, Paracoccus denitrificans und Thiobacillus denitrificans verantwortlich ist [3]. Ein erster Strukturvorschlag fur Ham d, basierte auf UVjVIS-, IR-und NMR-spektroskopischen sowie massenspektrometrischen Daten des demetallierten und veresterten Makrocyclus [4]. Dieser Vorschlag wurde jedoch durch Synthesestudien [5] und eine neue Interpretation der spektroskopischen Daten [6] revidiert. Der Metall-freie Ligand von Ham d, (3) ist von Wu und Chang [7] und in unserem Laboratorium [l] in racemischer Form synthetisiert worden, wobei wir durch unsere Synthese die bisher unbekannte relative Konfiguration von Ham d, (3) zweifelsfrei ermitteln konnten. Die vorliegende Arbeit beschreibt ausfuhrlich unsere Ergebnisse, iiber die wir in zwei vorlaufigen Mitteilungen berichtet hatten [l]. Battersby und Mitarbeitern [8] gelang es schliesslich, durch eine ca. 35 Schritte umfassende Totalsynthese des Metall-freien Liganden von Ham d, die

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“…1). Atoms C2 and C7 each carry a methyl group in the absolute configuration 2R, 7R as in siroheme, vitamin B,,, and factor F-430 [16]. Of particular interest is the origin of the 0x0 groups in positions C3 and C8 under anaerobic conditions.…”

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confidence: 99%

Resolution of the nirD Locus for Heme d₁, Synthesis of Cytochrome cd₁, (Respiratory Nitrite Reductase) from Pseudomonas Stutzeri

Palmedo

Seither

Körner

et al. 1995

European Journal of Biochemistry

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The genetic organization of the nirD locus of Pseudomonas stutzeri ZoBell, necessary for a catalytically active cytochrome cd, (EC 1.9.3.2), was determined. The locus comprises the unidirectionally transcribed open reading frames nirFDLGH, downstream of nirMC of the nir gene cluster, and immediately upstream of the norCB operon encoding nitric oxide (NO) reductase (EC 1.7.99.7). Notable sequence relatedness was found between NirF and cytochrome cd, (NirS), within NirDLGH, and between NirM and NirC, suggesting several gene duplication events in this region. The derived NirF protein (391 amino acids, Mr 43 137) has 23.8% identity (51.1 % overall similarity) with NirS, but lacks the N-terminal hemec-binding domain of NirS.Insertional mutagenesis of the five open reading frames resulted in the loss of respiratory nitrite reductase activity in vivo and in vitro. Mutant strains, when induced with nitrate for denitrification, synthesized a periplasmic cytochrome cd, lacking heme d,. The defect was caused by the inability of the cell to synthesize heme d,. The nirD locus is proposed to encode a multimeric and multifunctional enzyme complex involved in the synthesis of heme d,.Mutations in nirFDLGH lowered substantially the expression level of norCB. Nir-mutants, unable to generate NO in vivo, provide indirect evidence for an NO sensor and an inducer role of NO for its cognate reductase.

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A novel stereoselective synthesis of the macrocycle of haem d1 that establishes its absolute configuration as 2R,7R

Abstract: A novel route to isobacteriochlorins is developed that allows the stereoselective synthesis of the macrocycle of haem d, and so establishes its absolute configuration 2R,7R.

Cited by 16 publications

References 8 publications

Biosynthesis of the corrin macrocycle of coenzyme B12 in Pseudomonas denitrificans

Biosynthesis of the corrin macrocycle of coenzyme B12 in Pseudomonas denitrificans

Stereoselektive Synthese des Nitrit‐reduzierenden Cofaktors Häm d₁ ausgehend von Hämatoporphyrin

Resolution of the nirD Locus for Heme d₁, Synthesis of Cytochrome cd₁, (Respiratory Nitrite Reductase) from Pseudomonas Stutzeri

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A novel stereoselective synthesis of the macrocycle of haem d1 that establishes its absolute configuration as 2R,7R

Abstract: A novel route to isobacteriochlorins is developed that allows the stereoselective synthesis of the macrocycle of haem d, and so establishes its absolute configuration 2R,7R.

Cited by 16 publications

References 8 publications

Biosynthesis of the corrin macrocycle of coenzyme B12 in Pseudomonas denitrificans

Biosynthesis of the corrin macrocycle of coenzyme B12 in Pseudomonas denitrificans

Stereoselektive Synthese des Nitrit‐reduzierenden Cofaktors Häm d1 ausgehend von Hämatoporphyrin

Resolution of the nirD Locus for Heme d1, Synthesis of Cytochrome cd1, (Respiratory Nitrite Reductase) from Pseudomonas Stutzeri

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Product

Resources

About

Stereoselektive Synthese des Nitrit‐reduzierenden Cofaktors Häm d₁ ausgehend von Hämatoporphyrin

Resolution of the nirD Locus for Heme d₁, Synthesis of Cytochrome cd₁, (Respiratory Nitrite Reductase) from Pseudomonas Stutzeri