Riboside methyl 2,3-anhydro

In an attempt to synthesize 2-desoxy-L-ribose, Mukherjee and Todd68 treated methyl 2,3-anhydro-jS-L-ribopyranoside (LXXII) with sodium thiomethoxide and then reduced the amorphous product. The sulfur-free sirup thus obtained was inert to the action of periodate and is therefore methyl 3-desoxy-/3-L-riboside (ayn., methyl 3-desoxy-/3-L-xyloside) (LXXIV) rather than the desired 2-desoxy derivative. The methylthio intermediate (LXXIII) was consequently a 3-methylthio-L-xylose derivative rather than a 2-methylthio-L-arabinose compound. The presence of a trace of the latter, however, is not wholly excluded since the sirupy desoxypentoside (LXXIV) gave a feeble green coloration in the Keller-Kiliani test, a reaction generally accepted as being specific for 2-desoxy-sugars. 

Methyl 2,3-anhydro-/3-L-ribopyranoside (LVII) was caused to react with sodium methylmercaptide and thereafter the product was boiled under reflux with Raney nickel. The main desoxypentoside obtained was methyl 3-desoxy- 3-L-riboside (LVIII) and only traces of methyl 2-desoxy-/3-L-riboside were detected. 1 173 That the structure assigned to LVIII was correct was demonstrated by hydrolysis to the desoxy-... 

Application of the azidomercuration-demercuration procedure to the 5-ene (9) gave the 6- and 5-azides (10) and (11) in the ratio 1 4 (Scheme 1). The synthesis of azido-sugars via 2,3-anhydro-furanosides has been reported. Methyl 2,3-anhydro-0 -D-lyxofuranoside (12) gave the 3-azide (13) in 95% yield, and its 5-0-tosyl ester (14) gave the 3,6-diazide (15) in 84% yield. In contrast, the 2,3-anhydro-riboside (16) gave a mixture of the 2- and 3-azides (17) and (18) in the ratio 3 2. However, substitution at C-5 of (16) resulted in steric hindrance of the approach to C-3 and consequently the 5-tosylate (19) afforded the 2,6-... 

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). ... 

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