Glucopyranosid methyl 2-amino-2-deoxy

Such compounds have been identified amongst the products of deamination, followed by reduction, of methyl 2-amino-2-deoxy-a-and -/3-D-glucopyranoside.89a Two methyl 2-deoxy-2-(hydroxy-methyl)pentofuranosides, epimeric at C-2, were detected in each case, and the results of deuterium-incorporation experiments suggested that the primary product was epimerized, probably during reduction with sodium borohydride. However, in the writer s opinion, the configurations assigned to the primary and epimerized products are incorrect and should be reversed. 

Studies have revealed that the deamination of 2-amino-2-deoxy-D-glucosides is more complicated than previously supposed. It has been reported that methyl 2-amino-2-deoxy-a- and -/3-d-glucopyranoside give, in addition to 2,5-anhydro-D-mannose, methyl 2-deoxy-2-C-formyl-a- and -/S-D-ribofuranoside (for example, 97 to 98) in yields of 25 and 19%, respectively, under the experi-... 

B. Lindberg and O. Theander, Amino-deoxy- and deoxy-sugars from methyl 3-oxo-jS-d-glucopyranoside, Acta. Chem. Scand., 13 (1959) 1226-1230. 

RX. n-butyl bromide n-dodecanyl iodide cyclohexyl iodide ethyl bromo acetate methyl 2,3-di-O-acetyl-4-O-benzoyl-6-bromo-6-deoxy-ot-D-glucopyranoside methyl 2,3,4-tri-0-acetyl-6-deoxy-6-iodo-0 -D glucopyranoside l,2 3,4-di-0-isopropylidene-6-deoxy-6-iodo-a-D-galactopyranose methyl 2(R)-[(tert-butoxycarbonyl)amino]-3-iodo-propionate cyclic bis(trifluoromethyl)oxazolidinone bromide. 

According to Irvine and Hynd, the deamination of methyl 2-deoxy-2-(dimethylamino)-D-glucopyranoside with a hot solution of barium hydroxide provides methyl n-glucoside. The effect of conformation on the nitrous acid deamination of amino hexoses is further illustrated by the reaction of methyl 3-amino-4,6-0-benzylidene-3-deoxy-a-D-altropyrano-side (LXVII) which, on deamination with nitrous acid, provides a quantitative yield of methyl 2,3-anhydro-4,6-0-benzylidene-a-D-mannoside (LXVIII). The deamination of methyl 3-amino-3-deoxy-)8-D-altropy-ranoside, methyl epiglucosamine, gives a sirupy mixture. Similar treatment of methyl 2-amino-4,6-0-benzylidene-2-deoxy-a-D-altroside... 

Methyl 2-Deoxy-2-sulfoamino-j8-D-glucopyranoside Trisulfate and the Preparation of Tri-0-acetyl-2-amino-2-deoxy-a-D-glucopyranosyl Bromide, M. L. Wolfrom and T. M. Shen Han, . Org. Chem., 26, 2145-2146 (1961). 

Deoxymannojirimycin has been synthesized with excellent diastereoselec-tivity in a process based upon a palladium(II)-catalysed cyclization of an allylic alcohol 62 derived from D-mannitol. C-6 Homologues of 1-deoxynojirimycin and 1-deoxy-L-idonojirimycin (l,5,6-trideoxy-l,5-imino-D-gf/Mco- and -h-ido-heptitols) have also been prepared using palladium chemistry. In these reports the protected aminohex-l-enitol 63, derived from methyl a-D-glucopyranoside, was amino-carbonylated in the presence of palladium(II) chloride to afford a mixture of cyclized products whose composition was dependent upon the reaction conditions utilized. Two of these products, 64 and 65, were reductively transformed into the DNJ and 1-deoxy-L-idonojirimydn homolgues respectively 58,59... 

Methyl 6-deoxy-6-hydroxyamino-a-D-glucopyranoside has been synthesized by oxidation of the 6-amino-glycoslde to a 6-oxlme (HpOp-Na tungstate), and reduction (NaBH CN) 6 -N-hydroxy-... 

Methyl 4-amino-4-deoxy-a-D-glucopyranoside, A-268 Methyl 3-amino-3,4-dideoxy-a-D-xp/o-hexopyranoside, A-400 Methyl 3-amino-3,4-dideoxy-p-D-xp/o-hexopyranoside, A-400 Methyl 2-amino-2,4-dideoxy-a-DL-erpt/iro-pentopyranoside, A-411 Methyl 2-amino-2,4-dideoxy-a-DL-tAreo-pentopyranoside, A-412 Methyl 2,3-anhydro-4-deoxy-a-D-/pxo-hexopyranoside, A-555 Methyl 2,3-anhydro-4-deoxy-p-D-/yxo-hexopyranoside, A-555 Methyl 2,3-anhydro-4-deoxy-a-DL-/yxo-hexopyranoside, A-555 Methyl 2,3-anhydro-4-deoxy-a-DL-r 6o-hexopyranoside, A-558 Methyl 4-deoxy-2,3-di-0-methyl-a-D-xy/o-hexopyranoside, D-210 Methyl 4-deoxy-4-fluoro-a-L-arabinopyranoside, D-69 Methyl 4-deoxy-4-fluoro-p-L-arabinopyranoside, D-69 Methyl 4-deoxy-a-D-xy/o-hexopyranoside, D-210 Methyl 4-deoxy-p-D-xy/o-hexopyranoside, D-210 Methyl 4-deoxy-a-D- Areo-2-hexulofuranoside, D-223 Methyl 4-deoxy-p-D-fAreo-2-hexulofuranoside, D-223 Methyl 4-deoxy-p-DL-eryfAro-pentopyranoside, D-347 Methyl 4-deoxy-p-L-fAreo-pentopyranoside, D-350 Methyl 4-deoxy-a-D-ery Aro-pentopyranoside, D-347 Methyl 4-deoxy-p-D-ery /iro-pentopyranoside, D-347 Methyl 4-deoxy-p-L-ery /iro-pentopyranoside, D-347 Methyl 2,6-diacetamido-2,3,4,6-tetradeoxy-a-D-erp /iro-hexopyranoside, D-471... 

Methyl 6-deoxy-j8-D-glucopyranoside 2- and 4-toluene-p-sulphonates have been converted into the expected 2,3- and 3,4-oxirans, respectively, using a basic resin neither oxiran underwent migration under the reaction conditions used. An O-labelling study of the deamination of 2-amino-2-deoxy-D-mannose has shown that at least 62% of the D-glucose formed arises from 1,2-anhydro-D-glucopyranose, whereas the rest results from nucleophilic attack of water at C-2 of the diazonium ion. ... 

Condensation of the appropriate per-O-acetylated glycopyranosyl bromide with 4-aminobenzenethiol in the presence of sodium methoxide has been used to prepare 4-aminophenyl l-thio-j3-D-gluco-, -galacto-, and -xylo-pyranosides and 4-aminophenyl 2-acetamido-2-deoxy-1 -thio-jS-D-glucopyranoside. 4-Amino-phenyl l-thio-/3-D-glucopyranosiduronic acid was synthesized by condensation of methyl (2,3,4-tri-O-acetyI-a-D-glucopyranosyl bromide)uronate with 4-aminobenzenethiol, followed by saponification with sodium hydroxide. An attempt to obtain the l,2-ci5-l-thioaldopyranoside by reaction of 4,6-di-0-acetyl-2,3-0-carbonyl-a-D-mannopyranosyl bromide (191) with sodium 4-nitrobenzene-... 

CN methyl 6-[[[(2-chloroethyl)nitrosoamino]carbonyl]amino]-6-deoxy-a-D-glucopyranoside... 

Modification of the cyclohexenyl moiety has been carried out by use of the cyclohexadiene epoxides 243 and 244, which were coupled with methyl 4-amino-4-deoxy- and -4,6-dideoxy-0 -D-glucopyranoside (385a and 385b) to give the isomers (395 and 396). 

V-Deprotection of aminomethylenemalonate derivatives of 2-deoxyglu-copyranose (40, R = H, R1 = OMe, and R = OH, R1 = H,R2 = Ac, R3 = Et) by treatment with bromine or chlorine in chloroform afforded methyl 3,4,6-tri-0-acetyl-2-amino-2-deoxy-j3-D-glucopyranoside hydro-... 

M. W. Homer, L. Hough, and A. C. Richardson, Selective benzoylation of methyl 2-benzamido-2-deoxy-a-D-glucopyranoside A convenient preparation of derivatives of 2-amino-2-deoxy-D-galactose, /. Chem. Soc., Sect. C (1970) 1336-1340. 

Methyl 6-amino-6-deoxy-a-D-glucopyranoside derivatives 2c were synthesized in our laboratory by a somewhat different procedure [31]. 6-0-Sulfonyl or 6-bromo-6-deoxy derivatives of methyl a-o-glucopyranoside were substituted at C-6 by sodium azide. The 6-azido-6-deoxy intermediate was then treated by acyl chlorides in the presence of triphenylphosphine (Staudinger reaction) to afford amido derivatives which were finally de-O-acetylated to give 2c. The same reaction pathway allowed the preparation of 6-alkylamido-6-deoxy-D-glucopy-ranose derivatives, starting from o-glucose [31]. 

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