Synthesis of New Carbohydrate Phenyl- and Nitro-Aryl Ethers Derived from Simple Sugars

Abstract

Methyl 2-O-tosyl-β-L-arabinopyranoside (14). methyl 4-O-
tosyl-α-D-lyxopyranoside (15) and methyl 4-O-tosyl-α-L-rhamnopyranoside
(16) were prepared from their corresponding
isopropylidene-tosyl derivatives (11-13), from which upon epoxidation
with sodium methoxide in methanol. their corresponding anhydro
compounds (17), (19) and (20) were obtained. Reaction of
anhydro compounds (17), (19) and (20) with sodium phenolate in
refluxing DMF afforded methyl 3-O-phenyl-β-L-xylopyranoside
(21), methyl 4-O-phenyl-α-D-lyxopyranoside (23) and methyl 3-
O-phenyl-α-L-idopyranoside (24), respectively.
Periodata cleavage of methyl-β-D-glycopyranoside (31), methyl
β-D-galactopyranoside (32) and methyl β-D-mannopyranoside (33).
all gave "dialdehyde" (34). Cyclization, with nitromethane and
sodium methoxide, of the dialdehyde (34) led to an aci-nitrocondensation
product, from which methyl 3-nitro-3-deoxy-β-D-glucopyranoside
(36) was obtained. The 4,6-O-benzylidene derivative
(37) was obtained from (36) and converted to its 2-O-acetate (38).
The Schmidt-Rutz reaction of (38) afforded methyl 4,6-O-benzylidene-
2,3-dideoxy-3-nitro-β-D-erythrohexose-2-enide (39). Reaction
of hydrogen peroxide in a weakly alkaline medium with
nitroolefinic sugar (39) led to methyl 2,3-anhydro-4,6-O-benzylidene-
3-C-α-D-allopyranoside (40). Reaction of anhydro compound
(40) with phenoxide, α-naphthoxide and β-naphthoxide ions gave
methyl 4,6-O-benzylidene-3-nitro-2-O-phenyl-β-D-mannopyranoside
(41), methyl 4,6-O-benzylidene-3-nitro-2-O-α-naphthyl-β-D-mannopyranoside
and methyl 4,6-O-benzylidene-3-nitro-β-naphthyl-
β-D-mannopyranoside (43), respectively.