Allose derivative

Another method of synthesis of derivatives of 3-methyl-D-glucose lies in the scission of the anhydro-ring of 2,3-anhydro-D-allose derivatives with sodium methoxide, when the entry of the methoxyl group is accompanied by a Walden inversion on C3.82... 

Carbohydrates.—The acid (87), an intermediate in the synthesis of oxaprostaglandin derivatives from D-ribofuranose sugars,84 is obtained from the aldehyde (88) and the sodium salt of (79). The condensation of 2,5-anhydro-D-allose derivatives with (89) gave the expected products (90).85 Similarly, 1,4-furanoses (91) afford (92).86 These unsaturated halides are useful intermediates for further modifications. 

In their pioneering work. Just and co-workers have described many interesting transformations of the Diels-Alder adducts of furan to methyl nitroacrylate (77 + 77 ) and to dimethyl acetylenedicarboxylate (53). The mixture of racemic adducts 77 + 77 was hydroxylated into the exo-cis-diols 125 + 125 , separable by crystallization. Treatment of the isopropylidene acetal obtained from 125 with diazabicyclo[5.4.0]undec-5-ene (DBU) gave a high yield of alkene 126. Ozonolysis followed by a reductive work-up with dimethylsulfide, then with NaBH4, gave a mixture of epimeric triols 127. Cleavage with sodium periodate afforded 2,5-anhydro-3,4-0-isopropylidene-DL-allose (128) in 15 % yield, based on methyl 2-nitroacrylate used. TTie same allose derivative was obtained from adduct 53. ... 

R. U. Lemieux Application of nuclear magnetic resonance to problems of structure, configuration, and conformation in carbohydrate chemistry J. S. Brimacombe Synthesis of some naturally occurring allose derivatives and some associated chemistry... 

T. Uryu, K. Kitano, and K. Matsuzaki, Ring-opening polymerization of 5,6-anhydro-glucose and 5,6-anhydro-allose derivatives. Effect of substitution or configurational difference at the position of sugar monomers on polymerization behavior, J. Polym. Sci., Part A Polym. Chem., 20 (1982) 2181-2194. 

Two-step syntheses of D-glucose, D-mannose and n-allose derivatives... 

Cordova and co-workers have studied the double aldol reaction of benzyloxyacetaldehyde using various a-aminoacids as catalysts. With L-proline and hydroxy-L-proline a tetrose and the L-allose derivative 33 were obtained in 41 and 28% yield, respectively, and with an enantiomeric excess higher than 98% (O Scheme 26). As expected, with D-proline as catalyst, the corresponding D-allose derivative was obtained with the same ease in a one-pot operation [151]. 

Synthesis from o-allose A synthesis of the (3-lactam 15 has been reported from the D-allose derivative 11 (Scheme 1). Silylation of 11 followed by treatment with trichloroacetyl isocyanate afforded after crystallization the (3-lactam 12 (50%). Benzylation of 12 afforded 13, which underwent removal of the protecting groups to give 14. Cleavage of the vicinal diol group in 14, with sodium metaperiodate under standard conditions, led to the formation of a dialdehyde, which without isolation was reduced to give the (3-lactam derivative 15. 

Trummlitz and Moffatt prepared the tri-0-benzyl-/3-D-ribofuranosylgly-oxylic ester 45 from the 2,5-anhydro-o-allose derivative 54 and cyclized it... 

Cyclocondensation of the bicyclic 2,5-anhydro-D-allose derivative 312 with 2-(methylamino)thioethanol gave the 2-)8-D-ribofuranosylthiazolidine... 

W. Meyer zu Reckendorf and W. A. Boimer, Sulfur substitution products of amino sugars. VI. Synthesis of 2-amino-2-deoxy-3-thio-D-allose derivatives through thiazoline intermediates. Tetrahedron, 19 (1963) 1721-1725. 

Photolysis of 3-0-acetyl-3-C-methyl-l,2 5,6-0-isopropylidene-o -D-allo-furanose yielded the corresponding 3-deoxy-3-C-methyl-D-allose derivative (see... 

The synthesis of sugars by iterative, diastereoselective homologation of aldehydo-sugars with 2-trimethylsilylthiazole mentioned last year (see Vol. 19 p 5 ref. 11) has been extended up to nonose derivatives. The newly created chiral centre at C-2 invariably bore an erythro relationship to the C-3 substituent thus, D-glyceraldehyde led to the D-allose derivative (19)f and the meso-octitol (20) was obtained via the corresponding octose. 

Racemic 3-amino-sugars have been synthesized through hetero-Diels-Alder reactions of enaminones, Thus the major adduct from enamlnone (M6) and ethyl vinyl ether was converted to the M-deoxy-rlstosamlnide (M ) (Scheme 19). Racemic 5,6-dideoxy-5-amlno-allose derivatives such as (M8) have been constructed from the hetero-Dlels-Alder adducts of diene (M9) with acylnitroso... 

Using benzyloxyacetaldehyde in the trimerization process, the corresponding allose derivative 36 (R =OBn, R =CH20Bn) was obtained in 39% yield and 99% ee, with an important non-linear effect being detected [90]. This fact has been permitted the dynamic kinetic resolution processes of compounds of type anti-29 by... 

Bonafonsine, K"3.3 C35H42O6S4 Allose deriv., C"l.ll C35H42O9 Taxinine, T40.1 C35H43N5O... 

Carbohydrates have also been used as auxiliaries to control additions to nitroso diaiojdiiles, s de novo route to 5-amino-5,6-dideoxy-D-allose derivatives via 261 (Scheme 52) (see Chapter 16 and 18).1 2... 

The formation of 2,5-anhydropentose dibenzyl dithioacetals from pentose dibenzyl dithioacetals and that of 2,5-anhydro-D-allose derivatives via diazotiza-tion are discussed in Chapters 10 and 8, respectively. 

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