Glucitol 2,3,4,6-tetraacetate

Methyl 2-methyl-3-methylthio-4,6-benzylidene-/S-i>-idoside to methyl 2-methyl-3-de8Oxy-4,6-benzylidene-0-D-idoside Methyl 3-methylthio-5-L-xyloside to methyl 3-desoxy-/J-o-xyloside Ethyl thiol-D-ribonate tetraacetate to aldehydo-D-ribose tetraacetate Methyl thiol-D-gluconate pentaacetate to D-glucitol hexaacetate Ethyl tetraacetyl-0-D-glucopyranosyl xanthate to 1,5-anhydro-D-glucitol tetraacetate... 

Anhydro-D-glucitol tetraacetate was envisaged as opening to form the intermediate 32 which, through a series of rearrangements and cyclizations, yields 1,4-anhydro-D-glucitol, 1,4-anhydro-D-man-... 

Phenyl l-thio-0-D-glucopyranoside tetraacetate to 1,5-anhydro-D-glucitol... 

Both L-gulose12,13 (9) and D-gulose (d-9, see Ref. 10) have been oxidized with bromine to L- or D-gulonic acid, respectively (see Scheme 1). L-Gulose (9) has been prepared by a number of different procedures. Schemes 2 and 3 show two early procedures that afforded L-gu-lose, but the overall yields were low (<30%). In the first procedure12 (see Scheme 2), D-glucitol (10) was converted into 2,4-O-benzylidene-D-glucitol (11), which was then oxidized with lead tetraacetate to 2,4-O-benzylidene-L-xylose (12). Nitromethane was added to 12 to afford crystalline 13 in 50% yield. Hydrolysis of 13 provided 14, which was treated with sodium hydroxide, followed by sulfuric acid, to afford 9, which was isolated in 52% yield as the 2-benzyl-2-phenylhydrazone. 

Anhydro-L-gulono-1,4-lactone (62) was prepared100 in 62% yield by the platinum-catalyzed oxidation of 1,4-anhydro-D-glucitol. Methyl 3,4,5-tri-0-acetyl-2,6-anhydro-L-gulonate (63, R = H) was obtained from D-glucuronic acid by way of the tetraacetate (63, R = OAc) and the thioglycoside101,102 (63, R = SPh) (76%), followed by reduction in the presence of Raney nickel to afford 63 (R= H) (68%). 

Oxepane (seven-membered) rings (1,6-anhydrohexitols)52 have been prepared from the 3,4-isopropylidene acetals of D-mannitol, D-glucitol, and L-iditol, by way of alkaline hydrolysis of the corresponding 1,2 5,6-dianhydrides. The ring structures of the products were established through periodate oxidation and lead tetraacetate oxidation the requisite amount of formic acid was produced, and 3 equivalents of lead tetraacetate were consumed. No inversions at any of the asymmetric centers were involved in the reactions conducted, so the oxepanes had retained the configurations of the starting hexitols. 

Reference alditol acetates elute from the BPX-70 column in the following order erythritol triacetate, 2-deoxyribitol tetraacetate, rhamnitolpentaacetate, fucitolpentaacetate, ribitol pentaacetate, arabinitol pentaacetate, xylitol pentaacetate, 2-deoxyglucitol hexaacetate, allitol hexaacetate, mannitol hexaacetate, galactitol hexaacetate, glucitol hexaacetate, and rnyo-inositol hexaacetate. Their identification can be verified by using individual standards. 

The same tetraacetate (LXXI) was desulfurized, with Raney nickel to 2,3,4,6-tetra-0-acetyl-l,5-anhydro-D-glucitol (LXXIV). The requirement of a reactive halogen atom (in the carbohydrate component) rather limits the scope of this synthesis, but some further examples were supplied by Gehrke and Kohler in 1931. The reaction of 2,3,4-tri-O-acetyl-a-D-xylo-... 

D-Glucitol (sorbitol) hexaacetate, n-inannitol hexaacetate 0-D-Glucopyranose pentaacetate a-D-Arabinopyranose tetraacetate... 

The inner etherification induced in the sorbitol and D-mannitol structures during polyester formation, made a study of their inner ethers or anhydrides a matter of practical significance. A new monoanhydride of sorbitol was described (21) and designated arlitan (from the initials of the Atlas Research Laboratory). Identification as 1,4-anhydro-D-glucitol was made by comparison of its sirupy tetramethyl ether with that obtained by acid anhydrization of Irvine s 2,3,5,6-tetramethyl-D-glu-citoP by oxidation of the tetramethyl ether to dimethyl-L-threaric acid [0-dimethyl-L-((iea tartaric acid] and identification as the crystalline diamide and by its behavior on oxidation with lead tetraacetate. ... 

Lead tetraacetate oxidation of 2,5-anhydro-l,6-di-0-benzoyl-D-glucitol gave a crystalline dialdehyde dihydrate.No dehydration or infrared... 

Alditols, Cyclitols and Derivatives Thereof. - 2,5 3,4-Dianhydro-D-altritol, 2,5-aohydro-3,4-0-(l,2-ethanediyl)-D mannitol, pentaerythritol tetraacetate, ribitol tetraacetate, xylitol tetraacetate, D-arabinitol tetraacetate, D, L-arabinitol tetraacetate, 2,4 3,5-di-0-isopropylidene-D-mannitol, 2 hexa-O-acetyl-D-mannitol, allitol hexaacetate, D-mannitol hexaacetate, D, L-mannitol hexaacetate, D-iditol hexaacetate, D, L-iditol hexaacetate, D, L-glucitol hexaacetate, D, L-altritol hexaacetate, L-galacto-D-galacto-decitol (which is C2-symmetric), 5 6-0-benzyl-2,3-0-[(S)-caniphanylidene]-l,4,5-tris-0-pivaloyl-D-myo-inositol, 6D-3,6-di-0-benzyl-l-0-[(S)-camphanyl]-2-deoxy-2,2-difluoro-4,5-0-isopropylidene- y< -inositol, cyclopentane 28. ... 

Di-0-ter -butyldimethylsilyl-3,4-0-isopropylidene-D-glucitol on Swem oxidation then treatment with samarium diiodide gives the L-cA/ro-derivative 68 together with a small amount of the myo-isomer. Compound 68 was further converted into its hexaacetate for characterization purposes as well as into conduritol F tetraacetate. ... 

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