Shortcut Synthesis of β-Cyclomannin from β-Cyclodextrin

Fukudome, Makoto; Shiratani, Tomonori; Nogami, Yasuyoshi; Yuan, De‐Qi; Fujita, Kahee

doi:10.1021/ol062239b

Cited by 4 publications

(4 citation statements)

References 19 publications

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“…The results show that the osmium-catalyzed cis -dihydroxylation of disaccharide derivatives 2,3-dideoxy-4- O -β- d -galactopyranosyl- d - erythro -hex-2-enopyranosides exhibit the same stereospecificity reported for the oxidation of the monosaccharide 2,3-dideoxy- d - erythro -hex-2-enopyranoside congeners: oxidation of 2,3-unsaturated α-glycosides leads to the formation of α-mannosides whereas the oxidation of the respective β-anomers yields β-allosides. 19…”

Section: Resultsmentioning

confidence: 99%

A Ferrier glycosylation/cis-dihydroxylation strategy to synthesizeLeishmaniaspp. lipophosphoglycan-associated βGal(1,4)Man disaccharide

et al. 2022

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Section: Resultsmentioning

confidence: 99%

A Ferrier glycosylation/cis-dihydroxylation strategy to synthesizeLeishmaniaspp. lipophosphoglycan-associated βGal(1,4)Man disaccharide

et al. 2022

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“…This model was proposed based on the similarity of the anomeric chemical shifts to those of cyclodextrin . A helical MMP structure should have a more‐hydrophilic exterior and a more‐hydrophobic interior than amylose, based on a comparison of cyclodextrins and cyclomannins (cyclic oligosaccharides of α‐(1→4)‐linked mannopyranose) . To test this hypothesis, TROESY NMR measurements were performed on MMP and (MMP+PA) in aqueous solution.…”

Section: Resultsmentioning

confidence: 99%

“…4)-linked mannopyranose). [47][48] To test this hypothesis, TROESY www.chembiochem.org 3.9 ppm) would be expected. Such crosspeaks are clear in NOE experiments between amylose and hydrophobic guest molecules.…”

Section: Structure and Stability Of Mmp And (Mmp + + Fa)c Omplexes Inmentioning

confidence: 99%

Structure and Stability of Carbohydrate–Lipid Interactions. Methylmannose Polysaccharide–Fatty Acid Complexes

et al. 2016

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We report a detailed study of the structure and stability of carbohydrate-lipid interactions. Complexes of a methylmannose polysaccharide (MMP) derivative and fatty acids (FAs) served as model systems. The dependence of solution affinities and gas-phase dissociation activation energies (Ea ) on FA length indicates a dominant role of carbohydrate-lipid interactions in stabilizing (MMP+FA) complexes. Solution (1) H NMR results reveal weak interactions between MMP methyl groups and FA acyl chain; MD simulations suggest the complexes are disordered. The contribution of FA methylene groups to the Ea is similar to that of heats of transfer of n-alkanes from the gas phase to polar solvents, thus suggesting that MMP binds lipids through dipole-induced dipole interactions. The MD results point to hydrophobic interactions and H-bonds with the FA carboxyl group. Comparison of collision cross sections of deprotonated (MMP+FA) ions with MD structures suggests that the gaseous complexes are disordered.

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“…Strained cyclic glycophanes containing glucal subunits 6 also represent potential cage molecules for the complexation of cations and small molecules. 7 Recently, we disclosed 8 the synthesis of bishemiketal intermediate 2 through an ozonolysis-diastereoselective reduction sequence on diolefin threo-1. 9…”

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confidence: 99%

Efficient Synthesis of Cyclic Glycolipid Analogues

Coste¹,

Gerber‐Lemaire²

2007

Synlett

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A straightforward approach to macrocyclic structures containing deoxysugar subunits was developed through the functionalization of a bishemiketal. The choice of the length and the nature of the linkers can provide macrocycles with diverse rigidities and polarities.Carbohydrate-containing macrocycles and analogues represent highly interesting molecules in view of their diverse architectures and promising biological properties. 1 For instance, rigid cyclic glycolipids containing a phenylene-1,4-diamine subunit 2 have been prepared and may be used for modeling carbohydrate-carbohydrate interactions at interfaces relevant to cell-cell adhesion and communication. Butane-1,4-diol-linked cyclic neooligoaminodeoxysaccharides 3 have been synthesized for studying the RNA-small molecules interactions and for their ability to be superior binders for RNA than natural aminoglycosides. Carbohydrate macrocycles may also be useful as functional molecular pores. 4 It has been reported by Bundle et al. 5 that tethered analogues of trisaccharide epitopes display enhanced affinity for the binding to a monoclonal antibody. Strained cyclic glycophanes containing glucal subunits 6 also represent potential cage molecules for the complexation of cations and small molecules. 7 Recently, we disclosed 8 the synthesis of bishemiketal intermediate 2 through an ozonolysis-diastereoselective reduction sequence on diolefin threo-1. 9This derivative was then efficiently converted into several amino-functionalized polyketides. Polyketide-like macrolides were also efficiently prepared from diolefin 1 (Scheme 1). 10 We report here the straightforward conversion of 2 into analogues of carbohydrate-containing macrocycles.Our strategy for the preparation of macrocyclic structures was based on the double functionalization of the hemiketal moieties of 2 through a C-glycosylation reaction followed by biscoupling with a linker to close the macrolide. Peracetylation of 2, followed by treatment with allyltrimethylsilane and BF 3 ·OEt 2 , under diluted conditions, 11 afforded the bisallyl derivative 4 in 71% yield (two steps), as a single isomer (Scheme 2). The equatorial arrangement of the substituents at C(2¢¢, 2¢¢¢), C(4¢¢, 4¢¢¢) and C(6¢¢, 6¢¢¢) was established by 2D NOESY experiment.Transformation of diolefin 4 into the corresponding diol, followed by coupling with biscarboxylic acids 12 failed to provide the corresponding cyclic bislactones. Alternatively, ozonolysis of 4 followed by oxidation of the resulting aldehyde moieties, in the presence of NaClO 2 , gave diacid 5 in 35% yield (three steps). A biscoupling reaction with linear polyamines such as pentane-1,5-diamine and nonane-1,9-diamine, using PyBOP (benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate) as Scheme 1 Preparation of amino-functionalized polyketides OH OH OP PO threo-1 P = BOM O OH PO OH OH O OP OH 2 NH 2 NH 2 OH NH 2 OH OH OH OH 3 ref. 8 55% Scheme 2 Synthesis of macrocyclic diamides. Reagents and conditions: (a) Ac 2 O, pyridine, DMAP (cat.); (b) H 2 C=CHCH 2 SiMe 3 ,

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Shortcut Synthesis of β-Cyclomannin from β-Cyclodextrin

Cited by 4 publications

References 19 publications

A Ferrier glycosylation/cis-dihydroxylation strategy to synthesizeLeishmaniaspp. lipophosphoglycan-associated βGal(1,4)Man disaccharide

A Ferrier glycosylation/cis-dihydroxylation strategy to synthesizeLeishmaniaspp. lipophosphoglycan-associated βGal(1,4)Man disaccharide

Structure and Stability of Carbohydrate–Lipid Interactions. Methylmannose Polysaccharide–Fatty Acid Complexes

Efficient Synthesis of Cyclic Glycolipid Analogues

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