D-Mannopyranose derivatives

M. Kloostennan, M. P. de Nijs, and I. H. van Boom, Synthesis of 1,6-anhydro-2-0-trifluoro-methanesulphonyl-B-D-mannopyranose derivatives and their conversion into the corresponding 1,6-anhydro-2-azido-deoxy-p-D-giucopyranoses A convenient and efficient approach, J. Car-bohydr. Qum. 5 215 (1986). 

Table IV. Rapid Glycosidations on 1-0-Tosyl-D-Mannopyranose Derivatives ...

When D- and L-sorbose were mixed with hydrogen fluoride in liquid sulfur dioxide CC-D-sorbopyranose-a-L-sorbopyranose l,2 2,r-dianhydridc was formed preferentially, and similar treatment of D-sorbose and D-fructose afforded p-D-fructopyianose-a-D-sorbopyianose l,2 2,r-dianhydride. Some 1,3-anhydro-P-D-mannopyranose derivatives have been prepared by conventional means. and the NMR spectra of some 1,3-anhydro-P-L-rhamnopyranose and -P-D-mannopyranose ethers are covered in Chapter 21. 

Table IV. Comparison of Anomeric Proton (Hi) Chemical Shifts for Free and Acetylated D-gluco and D-mannopyranoses With Those of Related 2-Deoxy Sugar Derivatives. Effect of Replacing an Axial or an Equatorial C2-Methylene Proton With a Hydroxy or Actetoxy Substituent...

As 2-amino-2-deoxy-D-mannose is tumorstatic and 2-acetamido-2-deoxy-D-mannose 6-phosphate is an obligatory intermediate in the biosynthetic pathway to sialic acid, displacement of the essential OH-6 with a fluorine atom should be interesting from the biological viewpoint. 2-Acetamido-1,3,4-tri-0-acetyl-2,6-dideoxy-6-fluoro-D-mannopyranose (see Table 111 in Section 11,3) and its O- and A,0-deacetyl derivatives were prepared the first compound showed weak anticancer activity. 

It was found possible to saponify ovomucoid with sodium hydroxide and to methylate simultaneously with methyl Bulfate, the carbohydrate residue thereby forming an N-acetyl methyl derivative.14 Hydrolysis of this material yielded N-acetyl-3,4,6-trimethyl-D-glucosamine (7 moles) (LIVJ, D-mannopyranose (2 moles) (LV), 3,4,6-trimethyl-D-mannopy-ranose (1 mole) (LVI), and tetramethyl-D-galactopyranose (1 mole) (LVII). 

Thymidine 5 -(a-D-glucopyranosyl pyrophosphate) (4) and the analogous D-galactose derivative have been isolated from extracts of Pasteurella pseudo tuberculosis.102 The ester of thymidine 5 -pyro-phosphate with a-D-mannopyranose was found in an extract of Strep-tomyces griseus,14,103 and the occurrence of the D-ribosyl ester in the... 

Anhydro sugar derivatives that have the two reacting groups held in the required anti-periplanar (diaxial) orientation afford oxi-ranes very readily. Thus, l,6-anhydro-2-0-p-tolylsulfonyl-/3-D-gluco-pyranose (3) yields l,6 2,3-dianhydro-/3-D-mannopyranose (4) within... 

Nonphysiological compounds have also been described as influencing the overall metabolism of sialic acid. Administration of ethanol (2 g/kg) to rats significantly decreases the sialic acid content of brain tissue.246 Convulsions induced by pentylenetetrazole (6,7,8,9-tetrahy-dro-5/f-tetrazoloazepine) are accompanied by a diminution in the rate of biosynthesis of polysialogangliosicles GT, and GQn, in rat brain.227 Such ManNAc analogs as 2-acetamido-l,3,4,6-tetra-0-acetyl-2-deoxy-D-mannopyranose or the 2-(trifluoroacetamido) derivative lead to a marked lowering of the incorporation of radioactivity from labelled ManNAc into glycoconjugate sialic acids of murine, erythroleukemia (Friend) cells.247... 

Ammonium fluoride itself is not widely used, however, sporadic reference to it exists.187 Tetramethylammonium fluoride gives very good yields of the fluoro derivative 2 on reaction with l,6-anhydro-3,4-di-0-benzyl-2-0-(trifluoromethanesulfonyl)-/l-D-mannopyranose (1) in... 

The deamination of methyl 3-amino-3-deoxy-/3-D-altropyranoside was studied in 1934, but the products were not fully characterized.14411 The syrupy product was converted into a methylated derivative that had an elemental analysis corresponding to that calculated for a methyl tetramethylhexoside. The conditions used for methyl-ation would have opened an epoxide ring. Methyl 2,3-anhydro-4,6-0-benzylidene-a-D-mannopyranoside precipitated quantitatively from solution when the corresponding 3-amino-3-deoxyaltroside derivative was deaminated in aqueous medium.145 Epoxide formation was likewise reported to be quantitative in the deamination of the analogous 2-amino-2-deoxyaltroside.83 145 On deamination, 4-amino-l,6-anhydro-4-deoxy-/3-D-mannopyranose also gave an epoxide, namely, 1,6 2,3-dianhydro-/3-D-talopyranose, in unspecified yield.146... 

The formation of this pyrazine derivative results from a secondary reaction between the free monosaccharide and ammonia. Its formation involves loss of the asymmetry at C-l and C-2 of the free sugar, and thus the same heterocycle resulted from the ammonolysis of l,2,3,4,6-penta-0-nicotinoyl-/3-D-mannopyranose.34... 

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