Synthetic Methods in Bile Pigment Chemistry

Gossauer, Albert

doi:10.1002/ijch.198300024

Cited by 4 publications

(2 citation statements)

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“…As alluded to briefly in section , some CBCR-GAF domains modify the PCB chromophore even into a rubinoid-type compound without any further modification/isomerization of the chromophore. This happens via a nucleophilic attack of a second cysteine (in addition to the Cys required for covalent binding) to the central position C10, thereby forming a second covalent bond and converting the C10–C11 double bond into a cysteine-substituted single bond. , PVB, PUB, and also the rubinoid compounds have been synthesized chemically but were never employed in phytochrome assembly experiments.…”

Section: Bilin-binding Red-light-sensitive Photoreceptorsmentioning

confidence: 99%

“…This happens via a nucleophilic attack of a second cysteine (in addition to the Cys required for covalent binding) to the central position C10, thereby forming a second covalent bond and converting the C10–C11 double bond into a cysteine-substituted single bond. 54 , 64 PVB, PUB, and also the rubinoid compounds have been synthesized chemically 94 but were never employed in phytochrome assembly experiments.…”

Section: Bilin-binding Red-light-sensitive Photoreceptorsmentioning

confidence: 99%

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The Red Edge: Bilin-Binding Photoreceptors as Optogenetic Tools and Fluorescence Reporters

et al. 2021

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This review adds the bilin-binding phytochromes to the Chemical Reviews thematic issue “Optogenetics and Photopharmacology”. The work is structured into two parts. We first outline the photochemistry of the covalently bound tetrapyrrole chromophore and summarize relevant spectroscopic, kinetic, biochemical, and physiological properties of the different families of phytochromes. Based on this knowledge, we then describe the engineering of phytochromes to further improve these chromoproteins as photoswitches and review their employment in an ever-growing number of different optogenetic applications. Most applications rely on the light-controlled complex formation between the plant photoreceptor PhyB and phytochrome-interacting factors (PIFs) or C-terminal light-regulated domains with enzymatic functions present in many bacterial and algal phytochromes. Phytochrome-based optogenetic tools are currently implemented in bacteria, yeast, plants, and animals to achieve light control of a wide range of biological activities. These cover the regulation of gene expression, protein transport into cell organelles, and the recruitment of phytochrome- or PIF-tagged proteins to membranes and other cellular compartments. This compilation illustrates the intrinsic advantages of phytochromes compared to other photoreceptor classes, e.g., their bidirectional dual-wavelength control enabling instant ON and OFF regulation. In particular, the long wavelength range of absorption and fluorescence within the “transparent window” makes phytochromes attractive for complex applications requiring deep tissue penetration or dual-wavelength control in combination with blue and UV light-sensing photoreceptors. In addition to the wide variability of applications employing natural and engineered phytochromes, we also discuss recent progress in the development of bilin-based fluorescent proteins.

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Section: Bilin-binding Red-light-sensitive Photoreceptorsmentioning

confidence: 99%

Section: Bilin-binding Red-light-sensitive Photoreceptorsmentioning

confidence: 99%

The Red Edge: Bilin-Binding Photoreceptors as Optogenetic Tools and Fluorescence Reporters

et al. 2021

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Syntheses of Bile Pigments. Part 16. Synthesis of a vinyl‐substituted 2,3‐Dihydrobilinedione: Possible role of this new class of bile pigments in phycobilin biosynthesis

Gossauer

Nydegger

Benedikt³

et al. 1989

Helvetica Chimica Acta

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The total synthesis of racemic cis-2,3,18',18*-tetrahydroprotobiliverdin I X a dimethyl ester (19b), which is identical with the dimethyl ester of rac-4, is described (Scheme 2). Under virtually neutral conditions, in solution, this bile pigment isomerized within a few min to racemic Z-phycocyanobilin dimethyl ester (rue-5b). Likewise, acid-catalyzed ally1 rearrangement of 3-vinyl-substituted cis-and trans-2,3-dihydrodipyrrin-1 (10H)-ones l l c and 13c, respectively, yielded the corresponding ethylidene derivatives. In this case, however, the E-isomer was formed stereoselectively from both substrates. The above results prove that, if protobiliverdin

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Reactivity of Pyrrole Pigments, VIII. Preparation of 5(2H)‐Dipyrrylmethanones from 5(1H)‐Pyrromethenones by Reduction with Sodium Dithionite

et al. 1986

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5(1 H)-Pyrromethenones 3 have been reduced with sodium dithionite to give 5(2H)-dipyrrylmethanones 4 in very good yields. Some ofthe conditions to optimize this reduction have been studied. Reaktivitat von Pyrrolpigmenten, VlII'). -Darstellung von 5(2H)-Dipyrrylmethanonen aus S(1H)-Pyrromethenonen durch Reduktion mit Natriumdithionit5(1H)-Pyrromethenone 3 konnen mit Na2S204 in sehr guten Ausbeuten zu 5(2H)-Dipyrrylmethanonen 4 reduziert werden. Einige Reaktionsbedingungen wurden optimiert.Bile pigments of the urobilin type are prepared almost exclusively through a classical convergent synthesis2' involving the reduction of 5( 1H)-pyrromethenones to the corresponding 5(2H)-dipyrrylmethanones. This transformation can generally be achieved by catalytic hydr~genation~-~' or by alkali metal reduction3,',*) (commonly sodium amalgam). In both reduction methods the tetrahydro derivatives [3,4-dihydro-5(2H)-dipyrrylmethanones] are also obtained. In fact, in most cases, forcing the reduction conditions results in formation of these tetrahydro derivatives in good yields. In spite of its long history as a bleaching agent and vat dyeing reductant, sodium dithionite has been reported only recently as a reducing agent for carbonyl groups''. On the other side, the preparative use of sodium dithionite to reduce activated double bonds (conjugated carboxylic acids, esters and ketones) has been described'". In the bile pigment chemistry literature, sodium dithionite appears sporadically; i.e. in one low yield (3%) reduction of biliverdin IXu to bilirubin IXu"', and in relation to the chemistry of pentdyopents and propentdyopents derivatives'".In this paper, we report our results on the sodium dithionite (Na2S204) reduction of 5( 1H)-pyrromethenones (3) to 5(2H)-dipyrrylmethanones (4), and of the analogous 5-(arylmethylene)-l,5-dihydro-2H-pyrrol-2-ones (1) to 5-(arylmethyl)-1,5-dihydro-2H-pyrrol-2-ones (2). We also present our preliminary results on the reduction of verdins with Na2S204, in order to explain the low yields published for their reduction to rubins.The formula scheme shows the substrates tested (1 a -c, 3a -f) and the resulting derivatives (2a-c, 4a-f) reduced at the exocyclic double bond. Table 1 shows

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Synthetic Methods in Bile Pigment Chemistry

Abstract: The methodology of bile pigment synthesis including oxidative ring cleavage of porphin derivatives, total syntheses from pyrrole precursors and mutual transformation of bile pigments has been critically reviewed.

Cited by 4 publications

References 52 publications

The Red Edge: Bilin-Binding Photoreceptors as Optogenetic Tools and Fluorescence Reporters

The Red Edge: Bilin-Binding Photoreceptors as Optogenetic Tools and Fluorescence Reporters

Syntheses of Bile Pigments. Part 16. Synthesis of a vinyl‐substituted 2,3‐Dihydrobilinedione: Possible role of this new class of bile pigments in phycobilin biosynthesis

Reactivity of Pyrrole Pigments, VIII. Preparation of 5(2H)‐Dipyrrylmethanones from 5(1H)‐Pyrromethenones by Reduction with Sodium Dithionite

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