3.4- Anhydro-a-D-altropyranosid

Benzyl 3,4-anhydro-2,6-dideoxy-a-L-n 6o-hexopyranoside, A-591 Benzyl 3,4-anhydro-2-O-mesyl-6-O -trityl-a-D-altropyranoside, A-495 Methyl 2-0-acetyl-3,4-anhydro-a-D-arabinopyranoside, A-504 Methyl 2-0-acetyl-3,4-anhydro-p-L-arabinopyranoside, A-504 Methyl 3,4-anhydro-a-DL-allopyranoside, A-486 Methyl 3,4-anhydro-a-D-altropyranoside, A-495 Methyl 3,4-anhydro-a-D-arabinopyranoside, A-504 Methyl 3,4-anhydro-a-L-arabinopyranoside, A-504 Methyl 3,4-anhydro-p-L-arabinopyranoside, A-504 Methyl 3,4-anhydro-6-deoxy-p-L-ara6iwo-hex-5-enopyranoside, A-542 Methyl 3,4-anhydro-6-deoxy-n 6o-hex-5-enopyranoside, A-543 Methyl 3,4-anhydro-6-deoxy-a-L-ara >iwo-hex-5-enopyranoside, A-542 Methyl 3,4-anhydro-l,6-di-0-tosyl-a-i>tagatofiirajioside, A-701 Methyl 3,4-anhydro-l,6-di-0-tosyl-p-D-tagatofuraiioside, A-701 Methyl 3,4-anhydro-a-D-tagatofiiranoside, 9CI, A-701 Methyl 3,4-anhydro-p-D-tagatofuranoside, 9CI, A-701 Methyl 3,4-anhydro-6-0-trityl-a-i>altropyraiioside, A-495 Methyl l,6-di-0-acetyl-3,4-anhydro-a-D-tagatofuraiioside, A-701 Methyl l,6-di-0-acetyl-3,4-anhydro-p-D-tagatofiiraiioside, A-701 Methyl 2,6-di-0-acetyl-3,4-anhydro-a-DL-talopyranoside, A-711 Methyl 2,6 3,4-dianhydro-a-i>altropyranoside, D-491 Sarcobiose, S-14... 

Methyl 2,4-di-0-acetyl-3-am.ino-3,6-dideoxy-a-L-glucopyranoside, A-381 Methyl 4,6-di-0-acetyl-2,3-anhydro-a-D-allopyranoside, A-484 Methyl 3,4-di-0-acetyl-2,6-anhydro-a-D-altropyranoside, A-494 Methyl 3,4-di-0-acetyl-2,6-anhydro-p-D-altropyranoside, A-494 Methyl 3,4-di-O-acetyl-2,6-anhydro-5-deoxy-D-/yx -hex-5-enoate, A-541 Methyl 3,5-di-0-acetyl-l,4-anhydro-p-D-fructopyranoside, A-605 Methyl 2,5-di-0-acetyl-3,6-anhydro-a-L-gulofuranoside, A-640 Methyl 2,5-di-0-acetyl-3,6-anhydro-p-L-gulofuranoside, A-640 Methyl 2,5-di-0-acetyl-3,6-anhydro-a-L-idofuranoside, A-659 Methyl 2,5-di-0-acetyl-3,6-anhydro-p-L-idofuranoside, A-659 Methyl 3,4-di-0-acetyl-2,6-anhydro-a-D-idopyranoside, A-658 Methyl 3,4-di-0-acetyl-2,6-anhydro-p-D-idopyranoside, A-658 Methyl 3,4-di-0-acetyl-2,6-anhydro-a-D-inannopyranoside, A-678 Methyl 3,4-di-0-acetyl-2,6-anhydro-p-D-inannopyranoside, A-678 Methyl l,6-di-0-acetyl-3,4-anhydro-a-D-tagatofuranoside, A-701 Methyl l,6-di-0-acetyl-3,4-anhydro-p-D-tagatofuranoside, A-701 Methyl 3,4-di-0-acetyl-2,6-anhydro-a-D-talopyranoside, A-710 Methyl 3,4-di-0-acetyl-2,6-anhydro-p-D-talopyranoside, A-710 Methyl 2,6-di-0-acetyl-3,4-anhydro-a-DL-talopyranoside, A-711 Methyl 4,6-di-O-acetyl-3-azido-2,3-dideoxy-a-D-ara >m< -hexopyranoside, A-918... 

Methyl 3,4-di-0-acetyl-2,6-anhydro-a-D-altropyranoside, A-494 Methyl 3,4-di-0-acetyl-2,6-anhydro-p-D-altropyranoside, A-494 Methyl 3,4-di-0-acetyl-2,6-anhydro-a-D-idopyranoside, A-658 Methyl 3,4-di-0-acetyl-2,6-anhydro-p-D-idopyranoside, A-658 Methyl 3,4-di-0-acetyl-2,6-anhydro-a-D-mannopyranoside, A-678 Methyl 3,4-di-0-acetyl-2,6-anhydro-p-D-mannopyranoside, A-678 Methyl 3,4-di-0-acetyl-2,6-anhydro-a-D-talopyranoside, A-710 Methyl 3,4-di-0-acetyl-2,6-anhydro-p-D-talopyranoside, A-710 Methyl 2,6 3,4-dianhydro-a-D-altropyranoside, D-491 3,4,5,7-Tetra-0-acetyl-2,6-anhydro-1 -deoxy-D-g/wco-hept-l-enitol, A-529... 

A novel method of opening of oxiranes involves the use of (chlo-romethylene)dimethyliminium chloride (39) [see Section II,2c p. 250], monochlorodeoxy or dichlorodideoxy derivatives are obtained, depending upon the reaction conditions employed.83 Thus, methyl 2,3-anhydro-4,6-0-benzylidene-a-D-allopyranoside (110) reacts with 39 in 1,1,2,2-tetrachloroethane at room temperature to give, upon hydrolysis of the primary adduct 111 with an aqueous solution of sodium hydrogen carbonate, methyl 4,6-0-benzylidene-2-chloro-2-deoxy-3-0-formyl-a-D-altropyranoside (112). If a solution of 39 and 110 in 1,1,2,2-tetrachloroethane is heated at reflux temperature, methyl 3,4-0-benzylidene-2,6-dichloro-2,6-dideoxy-o -D-altropyrano-side (113) is obtained in high yield the n.m.r. spectrum of 113, like that of 47 (see Section II, 2c p. 250), showed the presence of two diastereoisomers which differed in the configuration of the benzyl-idene-acetal carbon atom. 

Inorganic Derivatives.- 1,6-Anhydro 2-chloro-2,4-dideoxy-4-(diphenylphosphoryl)-P-D-glucopyranose, the P-in-the-ring sugar analogues (27) and (28)," the natural arsenic-containing riboside (29), methyl 4,6-0-benzylidene-3-deoxy-3-C-triphenylstannyl-a-D-altropyranoside, two isomeric chromium(III) complexes with 1,3,5-triamino-1,3,5-trideoxy-cw-inositol in the one structure, the vanadium(in) complex (30),and the platinum(Il)-dithiocarbamate complex (31). ... 

Reaction of methyl 2,3-anhydro-4,6-0-benzylidene -a-D-allo- and manno-pyra-nosides with LiPPh2 afforded methyl 4,6-0-benzylidene-2-deoxy-2-C-diphenyl-phosphinyl-a-D-altropyranoside and methyl 4,6-0-ben2ylidene 3-deoxy-3-C-diphenylphosphinyl-a-D-altropyranoside respectively. Disaccharide phosphines, 6,6 -dideoxy-6,6 -bis(diphenylphosphinothioyl)-a,a-trehalose per-O-methyl and -benzyl ethers, have been prepared as chiral ligands for use with Rh(I) hydrogenation catalysts. ... 

Based on the fact that methyl 2,3-anhydro-a-D-mannopyranoside (II) is hydrolyzed17 by sodium methoxide to give, on subsequent methyla-tion, a mixture of two methyl trimethyl hexosides (methyl 3,4,6-trimethyl-a-D-altropyranoside and methyl 2,4,6-trimethyl-a-D-glucopyranoside) it was anticipated that the action of ammonia on II would follow essentially the same course. This was found to be the case, for with ammonia II yielded compounds which were converted to methyl 4,6-dimethyI-3-aeetamido-a-altropyranoside (III) and methyl 4,6-dimethyl-2-acetamido-a-D-glucopyranoside (IV) (10% yield). 

Neighboring-group participation by the vicinal, trans-acetoxyl group (see p. 125) serves to explain the abnormal behavior of methyl 4-0-acetyl-2,3-anhydro-6-0-benzyl- or -trityl-a-D-gulopyranoside with hydrogen chloride in acetone, or with 80% aqueous acetic acid, which give D-galactose, instead of the D-idose, derivatives.67 In the same way, 2-0-acetyl-3,4-anhydro-D-altropyranosides yield D-man-nosides, not D-idosides.9 6z(see p. 125). 

As might be expected, the nitrous acid deamination of methyl 2-amino-4,6-0-benzylidene-2-deoxy-a-D-altropyranoside (10) hydrochloride leads45,46 uniquely to methyl 2,3-anhydro-4,6-0-benzylidene-a-D-allopyranoside (11). The benzylidene group does not play an... 

J. W. Krajewski, P. Gluzinski, and A. Banaszek, X-Ray-investigation of benzyl 3,4-anhydro-2-0-mesyl-6-0-trityl-a-D-altropyranoside ring conformations in the 3,4-anhydropyranose system, Carbohydr. Res., 225 (1992) 1-9 and references therein. 

Treatment of an epoxide, namely methyl 2,3-anhydro-4,6-0-benzylidene-oi-D-allopyranoside (78, Scheme 21), with nitryl iodide using methanol as the solvent has been reported.123 Rather than the expected nitration, opening of the epoxide occurred to afford 30% of methyl 4,6-0-benzylidene-3-0-methyl-oi-D-glucopyranoside (79), 10% of methyl 4,6-0-benzylidene-2-0-methyl-a-D-altropyranoside (80), and a water-soluble material. The water-soluble material was later determined to be a mixture of the 2-0- (81) and 3-0-methyl (82) products, with the benzylidene acetal removed, a result consistent with a later study.124 Performing the reaction in the absence of the silver salt resulted solely in formation of the water-soluble product. The preponderance of the diequatorial product 81 is in violation of the Flirst-Plattner rule, which predicts more of the diaxial product. The authors explanation for the anti-Fiirst-Plattner addition is as follows. 

Methyl 4,6-0-benzyIidene-a-D-aItropyranoside. Triturate 4.0 g (0.015 mol) of the foregoing anhydro derivative in a mortar with a solution of 5 g of potassium hydroxide dissolved in 140 ml of water. Transfer the suspension to a round-bottomed flask and heat the mixture under reflux until all the solid has dissolved (about 28 hours). During this period solid material tends to creep up the inside of the flask surface shake periodically to re-suspend material. Remove the trace of insoluble matter which remains and neutralise the cooled filtrate with carbon dioxide (use phenophthalein as an indicator). Extract the solution with five 25 ml portions of dichloromethane, wash the combined extracts with a little cold water, dry over anhydrous sodium sulphate and remove the solvent under reduced pressure (rotary evaporator). Crystallise the syrup by scratching a small portion on a watch glass with ether stir the bulk syrup with ether and the seed crystals. Filter off and recrystallise the product from a small quantity of methanol to obtain 3.5 g (83%) of methyl 4,6-O-benzylidene-a-D-altropyranoside, m.p. 174 °C, [oc]d°+115° (c2 in CHCI3). 

In the limited number of examples where the trans- 1,2-diols would be diaxial if the compound adopted a chair conformation, mixtures are also usually obtained. To form dibutylstannylene acetals, conformational changes to skew, boat, or alternative chair conformations are required. Conversion to the boat is easy for l,6-anhydro-/3-D-glucopyranose149 and methyl a-D-idopyranoside, but may be more difficult for methyl 4,6-0-benzylidene-a-D-altropyranoside. 

Methyl 4,6-0-benzylidene-a- and jS-n-altropyranosides have been prepared from the corresponding n-glucosides, which were first converted into the 2,3-di-p-toluenesulfonates. Subsequent treatment of the p-toluenesulfonate with sodium methoxide in the cold afforded the 2,3-anhydro derivative. The latter was then converted into the n-altroside by means of boiling potassium hydroxide, Methyl 4,6-0-benzylidene-a-D-altropyranoside is very resistant to oxidation by periodate ion and does not form a cuprammonium complex — in accordance with the expected CA conformation (34). 

Methyl 3-azido-3-deoxy-2-0-p toluenesulfonyl-a-D-altropyranoside added to a soln. of p-toluenesulfonic acid in hot benzene, stirred and refluxed 4 hrs. -> 1,6-anhydro-3-azido-3-deoxy-2-0-p-toluenesulfonyl-/5-D-altropyranose. Y 74A%, F. e. s. H. Ku-zuhara, H. Ohrui, and S. Emoto, Carbohydrate Res. 11, 9 (1969). 

Me glycoside, 6-trityl Methyl 3,4-anhydro-6-0-trityl-a-D-altropyranoside [24558-68-7]... 

Benzyl 4-amino-2,3-anhydro-4-deoxy-a-D-lyxopyranoside, A-298 Benzyl 4-amino-2,3-anhydro-4-deoxy-p-L-lyxopyranoside, A-298 Benzyl 4-amino-2,3-anh.ydro-4-deoxy-p-D-ribopyranoside, A-331 Benzyl 4-amino-2,3-anhydro-4-deoxy-a-D-xylopyranoside, A-357 Benzyl 4-amino-2,3-anhydro-4-deoxy-p-L-xylopyranoside, A-357 Benzyl 2-amino-4,6-0 -benzylidene-2-deoxy-a-D-glucopyranoside 3-(dihydrogen phosphate), A-272 Benzyl 3-amino-3-deoxy-p-D-altropyranoside, A-165 Benzyl 5-amino-5-deoxy-a-D-arabinofuranoside, A-180 Benzyl 2-amino-2-deoxyglucopyranoside, B-13... 

Benzyl 2,3-anhydro-4-0-a-L-arabinopyranosyl-p-D-ribopyranoside, A-848 Benzyl 2,3-anhydro-4,6-0-benzylidene-a-D-allopyranoside, A-484 Benzyl 2,3-anhydro-4,6-0-benzylidene-p-D-gulopyranoside, A-639 Benzyl 2,3-anhydro-4,6-0-benzylidene-a-D-mannopyranoside, A-676 Benzyl 3,4-anhydro-2,6-dideoxy-a-L-r -hexopyranoside, A-591 Benzyl 2,3-anhydro-4- O - p-D-galactopyranosyl- p-D-ribopyranoside, G-173 Benzyl 2,3-anhydro-a-D-mannopyranoside, A-676 Benzyl 2,3-anhydro-p-D-mannopyranoside, A-676 Benzyl 3,4-anhydro-2-0-mesyl-6-0-trityl-a-D-altropyranoside, A-495 Benzyl 2,3-anhydro-4-0-methyl-p-D-ribopyranoside, A-693 Benzyl 2,3-anhydro-p-D-ery /iro-pentopyranosid-4-ulose, A-682 Benzyl 2,3-anhydro-p-L-eyy /iro-pentopyranosid-4-ulose, A-682 Benzyl 2,3-anhydro-a-D-ribopyranoside, A-693 Benzyl 2,3-anhydro-p-D-ribopyranoside, A-693 Benzyl 2,3-anhydro-p-L-ribopyranoside, A-693... 

Methyl 2,3-anhydro-6-0-trityl-a-D-allopyranoside, A-484 Methyl 3,4-anhydro-6-0-trityl-a-D-altropyranoside, A-495 Methyl 2,3-anhydro-6-0-trityl-a-D-gulopyranoside, A-639 Methyl 2,3-anhydro-5-0-trityl-a-D-lyxofuranoside, A-664 Methyl 2,3-anhydro-5-0-trityl-p-D-lyxofnranoside, A-664 Methyl 2,3-anhydro-6-0-trityl-a-D-mannopyranoside, A-676 Methyl 2,3-anhydro-5-0-trityl-a-D-ribofnranoside, A-690 Methyl 2,3-anhydro-5-0-trityl-p-D-ribofnranoside, A-690 Methyl 3,5-anhydro-p-D-xylofuranoside, A-728 Methyl p-D-apiofuranosyl-(l ->6)-p-D-glucopyranoside, A-784 Methyl arabinofuranoside, M-152... 

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