621. Branched-chain sugars. Part III. The introduction of branching into methyl 3,4-O-isopropylidene-β-<scp>L</scp>-arabinoside and the synthesis of<scp>L</scp>-hamamelose

Burton, J. S.; Overend, W. G.; Williams, N. R.

doi:10.1039/jr9650003433

Cited by 47 publications

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“…with Varían T-60 and HR-220 spectrometers using tetramethylsilane as an internal standard. Chemical shifts (5) are expressed in parts per million. The proton noise decoupled carbon-13 nmr spectra were recorded with a TNM PS-100 FT spectrometer.…”

Section: Methodsmentioning

confidence: 99%

“…9 We now wish to report the results of our studies on the addition of methylmagnesium halides and methyllithium to the methyl a-D-xyio-hexopyranosid-4-uloses 1 and 2, and on the application of the carbon-13 nmr spectroscopy for configurational assignments at the thus created branching carbon atom. Methyl 2,3-di-0-methyl-6-0-triphenylmethyl-«-D-xy/ohexopyranosid-4-ulose (1) and methyl 3-0-methyl-2-0me thy lsulfony 1-6-0-tr iphenylmethyl-n-D-xy/o-hexopyranosid-4-ulose (2) were synthesized by the oxidation of methyl 2,3-di-0-methyl-6-0-triphenylmethyl-«-D-glucopyranoside (4) and methyl 3-0-methyl-2-0-methylsulfonyl-6-O-triphenylmethyl-a-D-glucopyranoside (5) with dimethyl sulfoxide-acetic anhydride at 50-60°.…”

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confidence: 99%

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Synthesis of macrolide antibiotics. I. Stereospecific addition of methyllithium and methylmagnesium iodide to methyl .alpha.-D-xylo-hexopyranosid-4-ulose derivatives. Determination of the configuration at the branching carbon atom by carbon-13 nuclear magnetic resonance spectroscopy

Miljković¹,

Gligorijevic²,

Satoh³

et al. 1974

J. Org. Chem.

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137.9Formic Acid. A solution of 4c (50 mg) in 5 ml of trimethylammonium formate [bp 92" (18 mm)] was stirred for 2 hr at room temperature and left overnight. This solution was gently refluxed in a n oil bath for 3 hr until the reaction mixture was colored dark brown. When cooled, the separated crystals were collected and recrystallized from hexane-chloroform to colorless needles, m p 195-196". This was treated with 1 N sodium hydroxide form l-benzylbenzimidazole, m p and m m p with authentic sample 115". B.With Phosphoryl Chloride or Thionyl Chloride in Pyridine, To a solution of 4c (400 mg) in pyridine or pyridine-chloroform, phosphoryl chloride (5 ml) or thionyl chloride (4 ml) was added a t 0-5". After the reaction mixture was stirred for 1 hr a t room temperature, it was poured into ice-water. Extraction of the reaction mixture with benzene afforded 1-benzylbenzimidazole.C. With Lithium Aluminum Hydride-Aluminum Chloride. To an ether solution of 4c (450 mg), lithium aluminum hydride (50 mg) and aluminum chloride (25 mg) were added under stirring a t 0-5". After stirring overnight a t room temperature, the reaction mixture was treated with ethyl acetate and then with 0.1 N hydrochloric acid. Evaporation of the dried ether solution left a brownish syrup, which showed four spots on tlc ( R f 0.79, 0.45, 0.30, and 0.14), and the main spot ( R , 0.45) was found to be 1benzylbenzimidazole.Acknowledgment. Farkas, Tetrahedron. 28, 4197 (1972) All melting points were measured on a Mettler FP-1 melting point apparatus and are uncorrected. Gas chromatography was performed with a JGC-810 gas chromatograph and an OV-1 column was used at 180". CD and ORD curves were obtained on a Japan Spectroscopic Model J-20 recording polarimeter. Test solutions were prepared by dissolving about 2 mg of the sample in 1.5 ml of methanol, and quartz ceiis with an optical path of 1, 0.2, and 0.1 m m were used. Nmr spectra were measured with a Varian T-60 spectrometer and tetramethylsilane was used as an internal reference. Mass spectra were determined with a JEOL-O1S spectrometer by a direct inlet system at 75 eV.

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Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

Synthesis of macrolide antibiotics. I. Stereospecific addition of methyllithium and methylmagnesium iodide to methyl .alpha.-D-xylo-hexopyranosid-4-ulose derivatives. Determination of the configuration at the branching carbon atom by carbon-13 nuclear magnetic resonance spectroscopy

Miljković¹,

Gligorijevic²,

Satoh³

et al. 1974

J. Org. Chem.

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“…144°C; [a]D +41" (c 1.5); vmax. 3 Jdax.5eq 3.0 Hz, 4-Hax), and 1-74 (1 H, m, J4eq.4ax 13-87 J4eq.3 2-87 J 4 e q , ~e q 2-87 J4eq.sax 2. 5 Hz, 4-Heq), and 5-He,), 3.44 (3 H, s, OMe), 2.12 (1 H, m, J4ax,4eq 13.8, (Found: C , 61.2; H, 6.8; N , 5.6.…”

Section: Methyl 3-benzamido-2-o-benzoyl-34-dideoxy-a-~-ery T Hropento...mentioning

confidence: 97%

“…of this component is approximately five times greater for 1-H than for 3-H it was concluded that this isomer is the ' syn ' form of the phenylhydrazone (3).' (For the convention of assignment of ' syn ' and ' anti ' forms, see ref.…”

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confidence: 99%

Synthesis of 3-amino-3,4-dideoxysugars

Collins¹,

Overend²,

Racz³

1984

J. Chem. Soc., Perkin Trans. 1

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Sequential treatment of methyl 3,4-O-isopropylidencp-L-erythro-pentopyranosidulose (1 ) with aqueous sodium hydroxide and phenylhydrazine results in elimination of acetone and formation of 2s-methoxytetrahydropyran-3,4-dione 4-phenylhydrazone (7) as the main product. Similarly, methyl 6-deoxy-3,4-0-isopropylidene-2-t-lyxo-hexopyranosid -2 -u lose (2) was converted into 2Rmethoxy -6smethyltetrahydropyran -3,4-dione 4-phenylhydrazone (8). The effect of base on the related uloside, methyl 6-deoxy-2,3-O-isopropylidene-a-L-lyxo-hexopyranosid-4-ulose (1 6), resulted in the formation of 3-hydroxy-2-methyl-4H-py~an-4-one (maltol) (1 7). Compounds (7) and (8) have been converted into, respectively, 3-amino-3,4-dideoxy-~-erythro-pentopyranose (22) and 3-amino-3,4,6-trideoxy-~ribo-hexopyranose (25).Methyl glycosiduloses have been used extensively as intermediates in the modification of sugars. Such modification is usua1.l~ at the site of the hydroxy group in a methyl glycoside at which oxidation has been effected to produce the glycosidulose. In this paper, details are provided of a sequence of reactions which results in modification at C-3 and C-4 of a methyl glycopyranosid-2-ulose derivative.' This reaction sequence provides a convenient route for the preparation of aminosugars containing the -CH2CHNH2system, as occurs in some antibiotics.2The 2-ulosides investigated in this work were methyl 3,4-O-isopropylidene-~-~-er~t~r~-pentopyranos~duIose (1) and methyl 6-deoxy-3,4-0-isopropylidene-a-~-f~~xo-hexopyranoid-2-dose (2) which were prepared in good yields by well established procedures from, respectively, L-arabinose and ~-fucose.~ I H A 1 1 ) R 1 = R 2 = H J R 3 = O M e , X = O Configuration a t C-3-C-4, L-erythro 2 1 R' = Me , R2 = OMe , R3 = H X = 0 Configuration a t C-3-C-4, D-erythro ( 3 ) R' = R2 = H , R3 = OMe, X = NNHPhAtom numbering of the compounds in this paper is based on nome:nclature and the 'H n.rn.r. data

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“…Sharpless epoxidation of the enynols 83a and 83b. By Addition to CwO Groups About 50 publications dealing with the addition of acetylenes to aldosulopyranosides and -furanosides have been published since the first reports by Overend and co-workers in 1965 and 1970[155]. Mixtures of epimeric propargylic alcohols are expected, but the (mostly steric) influence of adjacent substituents may give diastereoselective addition.…”

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confidence: 99%