4-deoxy-4-fluoro-1,2-O-isopropylidene-β-D-xylo-hexulopyranose

Sarel-Imber, Meira; Bergmann, Ernst D.

doi:10.1016/s0008-6215(00)82426-x

Cited by 13 publications

(2 citation statements)

References 10 publications

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“…[20] Therefore, selectiono ft he reactioni si mportant for accessingp artially protected startingm aterials. To synthesize vinyl selenone-modified fructofuranoside and fructopyranoside, we selected methyl-3,4-anhydro-a-d-tagato-furanoside 1 [27] (Scheme 1) and 1,2-O-isopropylidene-3,4-anhydro-b-d-psicopyranoside 7 [28] (Scheme2), as these epoxides could be easily synthesized on ar elatively large scale from d-fructose in single isomeric forms. Thus, furanoside 1 was benzylated to afford dibenzyld erivative 2.T he epoxide ring of 2 was regioselectively opened by sodium phenyl selenide generatedf rom diphenyl diselenide and sodium borohydride [29a] to produce the corresponding b-hydroxy selenide derivative 3 in excellent yield.…”

Section: Resultsmentioning

confidence: 99%

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Vinyl Selenones Derived from d‐Fructose: A New Platform for Fructochemistry

2016

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d-Fructose, an inexpensive biomass precursor available on al arge scale, has been used for the generation of enantiomerically pure chemical entities. Construction of vinyl selenone moieties on cyclic skeletons of d-fructose led to the highly reactive synthetic intermediates comprisingo f an electron-deficient double bond along with an excellent leaving group. Reactions of these Michael acceptors with dif-ferent nucleophiles afforded aziridines, thiiranes,c yclopropanes, dihydrofurans, dihydroisoxazole, dibenzyloxymethylfuran, and isonucleosides in moderate to good yields. This powerful and practical route provides an ew platform for synthetic applicationso fr enewable biomass precursors and adds to the toolbox for chemists interested in new chemical entities. Supportinginformation for this article can be found under http:// dx.doi.org/10.1002/ajoc.201600183.I tc ontains 1 Ha nd 13 CNMR spectra of all new compounds, COSYs pectra( for 18 b, 20 a, 24,a nd 27 c), NOESY spectrum(for 17 c), 1D NOE difference spectra (for 18 b, 20 a,and 24), and ORTEP diagrams (for 15 h, 17 a, 22,and 30 b).populara ldoses such as d-glucose, d-mannose, d-ribose, dxylose, etc. Ac hiral ketones ynthesized from d-fructose [9] rapidly developed into an ew class of asymmetric epoxidation catalyst forthe epoxidation of olefins ( Figure 2). [10] Fructose-derived chiral 1,3-oxazolidine-2-thiones (OZTs) are also used as chiral substrates in coupling reactions ( Figure 2). [11] 1,5-Anhydro-dfructose( 1,5-AnFru) [12] and di-d-fructose dianhydrides (DFAs) [2, 13] are important precursors for the synthesis of new carbohydrate derivatives (Figure 2).We have been designing methodsf or accessing enantiopure oxaheterocycles, [14] carbocycles, [15, 16] aza-and thia-heterocycles, [16, 17] pyrroles, [18] and 1,5-disubstituted-1,2,3-triazoles [19] from monosaccharides. In line with the utilization of sugar molecules as "chiral pools"i ns ynthetic chemistry, [20] our strategy wast ou se highlyr eactive vinyl sulfone-and vinyl sulfoxide-modified carbohydrates, [21] which are powerful Michael acceptors ande fficient partners in cycloaddition reactions. [15, 19] More recently,w eh ave introduced vinyl selenone-modified carbohydrates as efficient Michael acceptors in diversity oriented synthesis (DOS) to generate complex molecular scaffolds. [22] The aryl selenoyl functionality of vinyl selenone plays ad ual role as an efficient electron-withdrawing group as well as al eaving group, allowing Michael addition followed by elimination in tandem fashion. [22] Although vinyl selenones are widely used in simple systems [23] and nucleosides, [24] vinyl selenones derived from carbohydrates have rarely been utilized partly because of the notoriously unpredictable stability of carbohydrate selenones or selenoxides. [25,26] Nevertheless,w e have designed and used stable vinyl selenone-modified furanosides for generating new molecules. [22,26] As d-fructose is now considered as an intermediate for generating small molecules such as 2,5-dimethylfuran, 5-hydroxymethy...

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Section: Resultsmentioning

confidence: 99%

“…As olution of compound 7 [28] (1.094 g, 5.41 mmol) was added to as uspension of 60 %N aH (0.28 g, 7.04 mmol) in dry DMF (15 mL) at 0 8Cu nder aN 2 atmosphere. After 0.5 h, benzyl bromide (1.028 mL, 8.66 mmol) was added dropwise to the above solution and the resulting solution was stirred at room temperature for 3h.…”

Section: Compoundmentioning

confidence: 99%

Vinyl Selenones Derived from d‐Fructose: A New Platform for Fructochemistry

2016

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Studies on Ketoses, 2. Spirocyclic Dihydropyranones from D‐Fructose

Lichtenthaler

Doleschal

1985

Liebigs Ann. Chem.

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Expedient reaction sequences have been developed to convert o-fructose into a diverse collection of spirocyclic dihydropyrandiols with 2S,3S (10, ll), 2R,5S (17, 18), and 2S,3R configuration (19), and of dihydropyranones 4 -7 with 2 s and 2R chirality. Due to the rigid attachment of pyranoid and dioxolane rings around a chiral spiro carbon which is to result in foreseeable regioand stereo-selectivities on additions to the olefinic and/or carbonyl double bonds, they represent highly versatile six-carbon synthons. -Key intermediates for their obtention are the long-known 3-O-benzoyl(8) and 3-0-tosyl derivatives (12) of 1,2-0-isopropylidene-~-fructopyranose, as well as the novel 4,5-di-Omesyl (9), the 3,4-di-O-tosyl (15), and the 3,4-di-O-benzoyl analogs 23. Introduction of olefinic unsaturation was effected with iodidelzinc in refluxing DMF (TipsonCohen procedure) or with triphenylphosphane/iodine/imidazole reagents, carbonyl groups were generated ilia PCC oxidation of the respective alcohols. The utilization of D-fructose as chiral source for the construction of complex, non-carbohydrate natural products in enantiomerically pure form is essentially negligible, recent accounts of the use of sugars as chiral substrates not even containing one example*). Only investigations towards the total synthesis of thermozymocidin3) and some pheromone-related spirobidioxanes4) have made use of o-fructose as starting material. This is undoubtedly due to the fact that the chemistry of fructose5) is less developed than that of the common aldoses which, in turn, has its cause in the adoption of all possible tautorneric forms in solution" and, hence, in product mixtures on reactions. Accordingly, the number of readily accessible, simple derivatives in a fixed tautomeric form is comparatively small: the tetraacetate7s*) and tetrabenzoate8) of 6-chloro-6-VCH Verlagsgesellschaft mbH, D-6940 Weinheim, 1985

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D

Collins¹

1998

Dictionary of Carbohydrates

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4-deoxy-4-fluoro-1,2-O-isopropylidene-β-D-xylo-hexulopyranose

Cited by 13 publications

References 10 publications

Vinyl Selenones Derived from d‐Fructose: A New Platform for Fructochemistry

Vinyl Selenones Derived from d‐Fructose: A New Platform for Fructochemistry

Studies on Ketoses, 2. Spirocyclic Dihydropyranones from D‐Fructose

D

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