Synthesis and properties of mesobilirubins XIIγ and XIIIγ and their mesobiliverdins

Sabido, Portia Mahal G.; Lightner, David A.

doi:10.1007/s00706-014-1160-6

Cited by 9 publications

(5 citation statements)

References 44 publications

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“…Much creative thinking and work has been devoted to the problem of bilin synthesis. − The inspection of the structure of bilirubin ( 1 ) reveals three repeating patterns of substitution, which are passed down to the various oxidation products. We color-coded these patterns in Scheme .…”

Section: Resultsmentioning

confidence: 99%

“…The 1942 landmark paper by Fischer and Plieninger demonstrated that bilirubin ( 1 ) can be synthesized in the laboratory . Since then, numerous creative synthetic approaches to tetracyclic bilin pigments have been reported. − De novo synthesis became an alternative source of pure bilins and allowed for site-specific high-content isotope labeling (e.g., 13 C and 14 C isotopologs of bilirubin , ). It follows that chemical synthesis can become the go-to method in the preparation of bilirubin oxidation products.…”

Section: Introductionmentioning

confidence: 99%

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A Platform for the Synthesis of Oxidation Products of Bilirubin

Mujawar,

Sevelda,

Madea

et al. 2024

J. Am. Chem. Soc.

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Bilirubin is the principal product of heme catabolism. High concentrations of the pigment are neurotoxic, yet slightly elevated levels are beneficial. Being a potent antioxidant, oxidative transformations of bilirubin occur in vivo and lead to various oxidized fragments. The mechanisms of their formation, intrinsic biological activities, and potential roles in human pathophysiology are poorly understood. Degradation methods have been used to obtain samples of bilirubin oxidation products for research. Here, we report a complementary, fully synthetic method of preparation. Our strategy leverages repeating substitution patterns in the parent tetracyclic pigment. Functionalized ready-to-couple γ-lactone, γ-lactam, and pyrrole monocyclic building blocks were designed and efficiently synthesized. Subsequent modular combinations, supported by metal-catalyzed borylation and cross-coupling chemistries, translated into the concise assembly of the structurally diverse bilirubin oxidation products (BOXes, propentdyopents, and biopyrrins). The discovery of a new photoisomer of biopyrrin A named lumipyrrin is reported. Synthetic bilirubin oxidation products made available in sufficient purity and quantity will support future in vitro and in vivo investigations.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Platform for the Synthesis of Oxidation Products of Bilirubin

Mujawar,

Sevelda,

Madea

et al. 2024

J. Am. Chem. Soc.

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“…This replacement, thus, seems to influence the packing arrangement of the ms-BR crystal. Besides this, the two bilirubinic compounds adopt a similar intramolecularly hydrogenbonded ridge-tile conformation shaped by, for example, a bifurcated N-HÁÁÁO(=C)ÁÁÁH-N hydrogen bond and an O-HÁÁÁO(=C) hydrogen bond (20)(21)(22)(23). Furthermore, both pigments exhibit similar solution properties and ms-BR thus has been used in various metabolic, photochemical, spectroscopic and pK a studies investigating BR as the breakdown product of heme catabolism (24)(25)(26)(27)(28)(29).…”

Section: Introductionmentioning

confidence: 99%

Crystal Effects on Mesobilirubin: A Combined NMR Spectroscopic and Density Functional Theory Study

Song

Matysik

Mark

2017

Photochem & Photobiology

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We report solid-state NMR investigations of crystal effects in powdered mesobilirubin-IXα, an open-chain tetrapyrrole that is structurally related to bilirubin-IXα but hydrogenated at the 3- and 18-vinyl groups. C and N cross-polarization magic-angle spinning (CP/MAS) NMR experiments were performed on the compound at natural abundance. To facilitate the spectral analysis, density functional calculations were carried out at the B3LYP/6-311G(d,p) level of theory, using an enneameric cluster to simulate the solid. The H, C and N chemical shift data calculated for the enneamer are in a good agreement with those observed in the experimental spectra, and the relative order of the calculated resonances was thus used to confirm the tentative assignments obtained mainly from the heteronuclear correlation spectra. The observed signal splittings of a small subset of the C resonances in the peripheral regions of the two terminal rings provide evidence for microcrystalline heterogeneity of the powdered compound.

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“…This reaction proceeded successfully when a p -methoxybenzyl group ( 1i ) was used as a protecting group for the nitrogen atom. Regarding the substituents at the α-position, an ethyl group was compatible with this reaction to produce γ-lactam 2j , which is a key building block for the synthesis of the natural pigment phycobilin and the antidiabetic drug glimepiride . An amide derived from cyclohex-1-ene-1-carboxylic acid also participated in this reaction, which resulted in the production of the bicyclic γ-lactam 2k in 60% yield.…”

mentioning

confidence: 99%

Synthesis of γ-Lactams from Acrylamides by Single-Carbon Atom Doping Annulation

Fujimoto,

Nakayasu,

Tobisu

2023

J. Am. Chem. Soc.

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Synthesis and properties of mesobilirubins XIIγ and XIIIγ and their mesobiliverdins

Cited by 9 publications

References 44 publications

A Platform for the Synthesis of Oxidation Products of Bilirubin

A Platform for the Synthesis of Oxidation Products of Bilirubin

Crystal Effects on Mesobilirubin: A Combined NMR Spectroscopic and Density Functional Theory Study

Synthesis of γ-Lactams from Acrylamides by Single-Carbon Atom Doping Annulation

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