Appel–Lee synthesis of glycosyl inositols, substrates for inositol dehydrogenase from Bacillus subtilis

Daniellou, Richard; Palmer, David R. J.

doi:10.1016/j.carres.2006.05.001

Cited by 12 publications

(10 citation statements)

References 31 publications

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“…Other sugar–inositol conjugates found in prokaryotic and eukaryotic cells include small molecules such as galactinol ( 25 ), mycothiol ( 26 ) and more complex molecules such as glycosylphosphatidylinositols (GPIs), − acting as anchors for cell-surface proteins. As the inositol moiety is tethered to the anomeric position of the sugar molecule, these compounds can usually be prepared via a straightforward O -glycosylation reaction onto the sugar donor. − The structural feature of an inositol–sugar conjugate with a highly functionalized sec–sec ether linkage as seen in InsAdA is, however, rarely reported in the literature and therefore a unique synthetic route was needed.…”

Section: Resultsmentioning

confidence: 99%

Inositol Adenophostin: Convergent Synthesis of a Potent Agonist of d-myo-Inositol 1,4,5-Trisphosphate Receptors

Döhle

Mills

et al. 2020

ACS Omega

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d-myo-Inositol 1,4,5-trisphosphate receptors (IP3Rs) are Ca2+ channels activated by the intracellular messenger inositol 1,4,5-trisphosphate (IP3, 1). The glyconucleotide adenophostin A (AdA, 2) is a potent agonist of IP3Rs. A recent synthesis of d-chiro-inositol adenophostin (InsAdA, 5) employed suitably protected chiral building blocks and replaced the d-glucose core by d-chiro-inositol. An alternative approach to fully chiral material is now reported using intrinsic sugar chirality to avoid early isomer resolution, involving the coupling of a protected and activated racemic myo-inositol derivative to a d-ribose derivative. Diastereoisomer separation was achieved after trans-isopropylidene group removal and the absolute ribose–inositol conjugate stereochemistry assigned with reference to the earlier synthesis. Optimization of stannylene-mediated regiospecific benzylation was explored using the model 1,2-O-isopropylidene-3,6-di-O-benzyl-myo-inositol and conditions successfully transferred to one conjugate diastereoisomer with 3:1 selectivity. However, only roughly 1:1 regiospecificity was achieved on the required diastereoisomer. The conjugate regioisomers of benzyl derivatives 39 and 40 were successfully separated and 39 was transformed subsequently to InsAdA after amination, pan-phosphorylation, and deprotection. InsAdA from this synthetic route bound with greater affinity than AdA to IP3R1 and was more potent in releasing Ca2+ from intracellular stores through IP3Rs. It is the most potent full agonist of IP3R1 known and .equipotent with material from the fully chiral synthetic route.

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Section: Resultsmentioning

confidence: 99%

Inositol Adenophostin: Convergent Synthesis of a Potent Agonist of d-myo-Inositol 1,4,5-Trisphosphate Receptors

Döhle

Mills

et al. 2020

ACS Omega

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“…(GlcNAc), [11][12][13] as well as 3-deoxy-d-manno-oct-2-ulosonic acid (KDO), [14] and the sugar alcohol myo-inositol. [15][16][17] This Review describes the uses and capabilities of MGE with N-acyl side chain modified mannosamines.I nt his context, understanding the biochemistry and biology of Neu5Ac is,t herefore,aprerequisite.…”

Section: Introductionmentioning

confidence: 99%

“…On the basis of this strategy, MGE has been successfully applied to other monosaccharides, including d ‐ N ‐acetylgalactosamine (GalNAc), d ‐ N ‐acetylglucosamine (GlcNAc), as well as 3‐deoxy‐ d ‐manno‐oct‐2‐ulosonic acid (KDO), and the sugar alcohol myo‐inositol …”

Section: Introductionmentioning

confidence: 99%

Metabolic Glycoengineering with N‐Acyl Side Chain Modified Mannosamines

2016

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In metabolic glycoengineering (MGE), cells or animals are treated with unnatural derivatives of monosaccharides. After entering the cytosol, these sugar analogues are metabolized and subsequently expressed on newly synthesized glycoconjugates. The feasibility of MGE was first discovered for sialylated glycans, by using N-acyl-modified mannosamines as precursor molecules for unnatural sialic acids. Prerequisite is the promiscuity of the enzymes of the Roseman-Warren biosynthetic pathway. These enzymes were shown to tolerate specific modifications of the N-acyl side chain of mannosamine analogues, for example, elongation by one or more methylene groups (aliphatic modifications) or by insertion of reactive groups (bioorthogonal modifications). Unnatural sialic acids are incorporated into glycoconjugates of cells and organs. MGE has intriguing biological consequences for treated cells (aliphatic MGE) and offers the opportunity to visualize the topography and dynamics of sialylated glycans in vitro, ex vivo, and in vivo (bioorthogonal MGE).

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“…B. für die Darstellung von sialylierten Glykanen mit fluoreszierenden Farbstoffen verwendet werden. Basierend auf dieser Strategie konnte MGE auch mit anderen Monosacchariden angewendet werden, einschließlich d ‐ N ‐Acetylgalactosamin (GalNAc), d ‐ N ‐Acetylglucosamin (GlcNAc) sowie 2‐Keto‐3‐desoxyoctonsäure (KDO) oder dem Zuckeralkohol Myoinositol …”

Section: Introductionunclassified

Metabolisches Glykoengineering mit N‐Acyl‐Seiten‐ ketten‐modifizierten Mannosaminen

2016

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Beim metabolischen Glykoengineering (MGE) werden Zellen und Tiere mit nichtnatürlichen Derivaten von Monosacchariden behandelt. Diese werden nach ihrer Aufnahme ins Zytosol metabolisiert und anschließend auf neusynthetisierten Glykokonjugaten exprimiert. MGE wurde zuerst für sialylierte Glykane realisiert, mit N‐Acyl‐modifizierten Mannosaminen als Vorstufen für nichtnatürliche Sialinsäuren. Voraussetzung ist die Promiskuität der Enzyme des Roseman‐Warren‐Biosyntheseweges. Diese tolerieren spezifische Modifikationen der N‐Acyl‐Seitenkette von Mannosaminderivaten, z. B. Elongation mit Methylen‐Gruppen (aliphatische Modifikationen) oder Einfügen reaktiver Gruppen (bioorthogonale Modifikationen). Nichtnatürliche Sialinsäuren werden in Glykokonjugate von Zellen und Organen integriert. MGE hat faszinierende biologische Konsequenzen für die behandelten Zellen (aliphatisches MGE) und ermöglicht die Visualisierung der Topographie und Dynamik der sialylierten Glykane in vitro, ex vivo und in vivo (bioorthogonales MGE).

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Appel–Lee synthesis of glycosyl inositols, substrates for inositol dehydrogenase from Bacillus subtilis

Cited by 12 publications

References 31 publications

Inositol Adenophostin: Convergent Synthesis of a Potent Agonist of d-myo-Inositol 1,4,5-Trisphosphate Receptors

Inositol Adenophostin: Convergent Synthesis of a Potent Agonist of d-myo-Inositol 1,4,5-Trisphosphate Receptors

Metabolic Glycoengineering with N‐Acyl Side Chain Modified Mannosamines

Metabolisches Glykoengineering mit N‐Acyl‐Seiten‐ ketten‐modifizierten Mannosaminen

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