Chemical synthesis of scyllo-inosamine and catabolism studies in Sinorhizobium meliloti

Schoffers, Elke; Gurung, Sing R.; Kohler, Petra R. A.; Rossbach, Silvia

doi:10.1016/j.bmc.2008.06.040

Cited by 10 publications

(6 citation statements)

References 37 publications

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“…Other inositol derivatives, the rhizopines scyllo-inosamine and L-3-O-methylscyllo-inosamine, have been termed nutritional mediators, because they represent exclusive carbon and nitrogen sources for the rhizobial strains that carry the rhizopine catabolism genes (26,36,38,43). Rhizopine and inositol catabolism are interrelated, because a functional inositol catabolic pathway was shown to be required for the catabolism of rhizopines (2,15,38). Clearly, inositol compounds and the ability to catabolize them play important nutritional or signaling roles in the symbiotic relationship between rhizobia and legume plants.…”

Section: Discussionmentioning

confidence: 99%

“…Rhizopines, produced by several symbiotic S. meliloti and Rhizobium leguminosarum bv. viciae strains, are inositol derivatives, namely, scyllo-inosamine and L-3-O-methylscyllo-inosamine (26,36,38,43). The ability to catabolize these inositol derivatives (rhizopines) has been shown to play a role in competition for nodule occupancy (35), but it seems that the ability to catabolize myo-inositol itself may also play a role in plant-bacteria interactions.…”

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Inositol Catabolism, a Key Pathway in Sinorhizobium meliloti for Competitive Host Nodulation

Kohler

Zheng

Schoffers

et al. 2010

Appl Environ Microbiol

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The nitrogen-fixing symbiont of alfalfa, Sinorhizobium meliloti, is able to use myo-inositol as the sole carbon source. Putative inositol catabolism genes (iolA and iolRCDEB) have been identified in the S. meliloti genome based on their similarities with the Bacillus subtilis iol genes. In this study, functional mutational analysis revealed that the iolA and iolCDEB genes are required for growth not only with the myo-isomer but also for growth with scyllo-and D-chiro-inositol as the sole carbon source. An additional, hypothetical dehydrogenase of the IdhA/MocA/GFO family encoded by the smc01163 gene was found to be essential for growth with scyllo-inositol, whereas the idhA-encoded myo-inositol dehydrogenase was responsible for the oxidation of D-chiro-inositol. The putative regulatory iolR gene, located upstream of iolCDEB, encodes a repressor of the iol genes, negatively regulating the activity of the myo-and the scyllo-inositol dehydrogenases. Mutants with insertions in the iolA, smc01163, and individual iolRCDE genes could not compete against the wild type in a nodule occupancy assay on alfalfa plants. Thus, a functional inositol catabolic pathway and its proper regulation are important nutritional or signaling factors in the S. meliloti-alfalfa symbiosis.The sugar alcohol inositol, or cyclohexanehexol, occurs in several different stereoisomers, of which the myo-form (Fig. 1, compound 1) is the most abundant (1). myo-Inositol plays important structural and signaling roles in animal and plant cells (22). In the environment, myo-inositol mainly occurs in the phosphorylated form and is involved in the phosphate cycle of terrestrial and freshwater ecosystems (41). The stereoisomers D-chiro-and scylloinositol have recently attracted attention, because they have shown therapeutic potentials for diabetes and Alzheimer's disease, respectively (11, 21). Although there is only limited knowledge about the metabolism of D-chiro-and scyllo-inositol (25, 50), the catabolism of myo-inositol has been studied in a variety of microorganisms, including some members of the Firmicutes (17, 46, 51), Enterobacteriaceae (4,19,40), and Rhizobiaceae (16,29). The myo-inositol catabolic pathway and its regulation are best understood in the Gram-positive bacterium Bacillus subtilis. The B. subtilis iol genes are organized in a divergon comprising iolABCDEFGHIJ and iolRS (47-49). In the proposed inositol catabolic pathway, the myo-inositol dehydrogenase oxidizes myoinositol to its corresponding ketone 2-keto-myo-inositol (2KMI), which is then further catabolized by the actions of IolE, -D, -B, -C, -J, and -A (Fig. 1). The inducer of the inositol catabolic pathway in B. subtilis is the product of the IolC reaction, 2-deoxy-5-keto-D-gluconic acid 6-phosphate (DKGP; compound 6 in Fig. 1), which antagonizes the binding of the IolR repressor to the iol promoter region (51).Sinorhizobium meliloti, the nitrogen-fixing symbiont of alfalfa, can use myo-inositol as the sole carbon source (15). The idhA-encoded myo-inositol dehydrogenase had been s...

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Inositol Catabolism, a Key Pathway in Sinorhizobium meliloti for Competitive Host Nodulation

Kohler

Zheng

Schoffers

et al. 2010

Appl Environ Microbiol

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“…syn ‐Adducts are isolated indirectly by inverting the alcohol of the anti product. Methods include the Mitsunobu reaction11–19 and the substitution of sulfonates 20–24. The preparation of cis ‐1‐amino‐2‐indanol is a notable industrial example and was carried out independently by researchers at Merck and Sepracor.…”

Section: Introductionmentioning

confidence: 99%

First isolation of disubstituted cis‐5,6‐dihydro‐1,10‐phenanthrolines. lipase‐mediated resolution of cis‐ and trans‐phenoxy alcohol isomers and assignment of absolute stereochemistry via cd and nmr spectroscopy

et al. 2012

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5,6-Dihydro-1,10-phenanthrolines can display axial and central chirality. In conjunction with the ligating properties of the diimino moiety, this class of compounds is of great interest to applications in supramolecular chemistry. We report the first preparation of cis-5,6-dihydro-1,10-phenanthroline derivatives by reacting triphenyl borate with the corresponding epoxide precursor. We found that solvent and temperature choice determined the stereoselectivity of the epoxide opening giving rise to the cis (14:1 dr) or trans (99:1 dr) product. Racemates of each stereoisomeric mixture, cis- and trans-phenoxy alcohol, were separated via highly enantioselective transesterifications with lipase PSCI from Burkholderia cepacia (97% ee, E > 200). Stereochemical assignments were carried out using CD and X-ray analyses in conjunction with NMR studies of α-methoxy-α-(trifluoromethyl)phenylacetic acid and α-methoxyphenylacetic acid esters.

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“…N-Boc-6-aminohexanol (1) was synthesized according to the published method (34). 1,3,4,5,6-Penta-O-benzyl-myoinositol (3) was synthesized according to literature method(35). mmol) in 20 mL anhydrous DCM cooled to -20°C was added N,N-diisopropylphosphoramidous dichloride (1.46 g, 7.24 mmol) and DIPEA (2.52 mL, 14.5 mmol), the mixture was allowed to stir at -5°C for 3 h. The solvent was then evaporated under vacuum, and the product was purified via silica gel chromatography (hexane -Et 3 N, 95:5) to give the desired product as a white solid (1.01g, 52%) 1.…”

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“…34 1,3,4,5,6-Penta-O-benzyl-myo-inositol (3) was synthesized according to a literature method. 35 O-Xylylene N,N-Diisopropylphosphoramidite. 36 To a solution of 1,2-benzenedimethanol 37 (1.00 g, 7.24 mmol) in 20 mL of anhydrous DCM cooled to −20 °C were added N,Ndiisopropylphosphoramidous dichloride (1.46 g, 7.24 mmol) and DIPEA (2.52 mL, 14.5 mmol), and the mixture was allowed to stir at −5 °C for 3 h. The solvent was then evaporated under vacuum, and the product was purified via silica gel chromatography (hexane/Et 3 N, 95:5) to give the desired product as a white solid (1.01 g, 52%): 1 H NMR (CDCl 3 ) δ 1.19 (m, 12H, CH 3 ), 3.57−3.66 (m, 2H, NCH), 7.29 (s, 4H, aromatic); 31 P NMR (CDCl 3 ) δ 150.0 (s).…”

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Synthesis of Biotinylated Inositol Hexakisphosphate To Study DNA Double-Strand Break Repair and Affinity Capture of IP₆-Binding Proteins

2015

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Inositol hexakisphosphate (IP6) is a soluble inositol polyphosphate, which is abundant in mammalian cells. Despite the participation of IP6 in critical cellular functions, few IP6-binding proteins have been characterized. We report on the synthesis, characterization, and application of biotin-labeled IP6 (IP6-biotin), which has biotin attached at position 2 of the myo-inositol ring via an aminohexyl linker. Like natural IP6, IP6-biotin stimulated DNA ligation by nonhomologous end joining (NHEJ) in vitro. The Ku protein is a required NHEJ factor that has been shown to bind IP6. We found that IP6-biotin could affinity capture Ku and other required NHEJ factors from human cell extracts, including the DNA-dependent protein kinase catalytic subunit (DNA-PKcs), XRCC4, and XLF. Direct binding studies with recombinant proteins show that Ku is the only NHEJ factor with affinity for IP6-biotin. DNA-PKcs, XLF, and the XRCC4:ligase IV complex interact with Ku in cell extracts and likely interact indirectly with IP6-biotin. IP6-biotin was used to tether streptavidin to Ku, which inhibited NHEJ in vitro. These proof-of-concept experiments suggest that molecules like IP6-biotin might be used to molecularly target biologically important proteins that bind IP6. IP6-biotin affinity capture experiments show that numerous proteins specifically bind IP6-biotin, including casein kinase 2, which is known to bind IP6, and nucleolin. Protein binding to IP6-biotin is selective, as IP3, IP4, and IP5 did not compete for binding of proteins to IP6-biotin. Our results document IP6-biotin as a useful tool for investigating the role of IP6 in biological systems.

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Chemical synthesis of scyllo-inosamine and catabolism studies in Sinorhizobium meliloti

Cited by 10 publications

References 37 publications

Inositol Catabolism, a Key Pathway in Sinorhizobium meliloti for Competitive Host Nodulation

Inositol Catabolism, a Key Pathway in Sinorhizobium meliloti for Competitive Host Nodulation

First isolation of disubstituted cis‐5,6‐dihydro‐1,10‐phenanthrolines. lipase‐mediated resolution of cis‐ and trans‐phenoxy alcohol isomers and assignment of absolute stereochemistry via cd and nmr spectroscopy

Synthesis of Biotinylated Inositol Hexakisphosphate To Study DNA Double-Strand Break Repair and Affinity Capture of IP₆-Binding Proteins

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Chemical synthesis of scyllo-inosamine and catabolism studies in Sinorhizobium meliloti

Cited by 10 publications

References 37 publications

Inositol Catabolism, a Key Pathway in Sinorhizobium meliloti for Competitive Host Nodulation

Inositol Catabolism, a Key Pathway in Sinorhizobium meliloti for Competitive Host Nodulation

First isolation of disubstituted cis‐5,6‐dihydro‐1,10‐phenanthrolines. lipase‐mediated resolution of cis‐ and trans‐phenoxy alcohol isomers and assignment of absolute stereochemistry via cd and nmr spectroscopy

Synthesis of Biotinylated Inositol Hexakisphosphate To Study DNA Double-Strand Break Repair and Affinity Capture of IP6-Binding Proteins

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Synthesis of Biotinylated Inositol Hexakisphosphate To Study DNA Double-Strand Break Repair and Affinity Capture of IP₆-Binding Proteins