Acetolysis of 2,4-O-benzylidene-D-xylo-hex-5-enitol derivatives

Article abstract of DOI:10.1016/0008-6215(93)84208-N

Acetolysis of (Z)-1-O-acetyl-2,4-O-benzylidene-5,6-dideoxy-6-C-(2,4-dichlorophenyl)-3-O-methanesulfonyl-D-xylo-hex-5-enitol afforded (E)-1,2,4-tri-O-acetyl-5,6-dideoxy-6-C-(2,4-dichlorophenyl)-3-O-methanesulfonyl-D-xylo- and -L-arabino-hex-5-enitol, 2-C-<(R)-acetoxy(2,4-dichlorophenyl)methyl>-3,6-di-O-acetyl-2-deoxy-4-O-methanesulfonyl-β-L-galacto-hexopyranosylbenzene and 6-O-acetyl-2-deoxy-2-C-<(R)-(2,4-dichlorophenyl)hydroxymethyl>-4-O-methanesulfonyl-β-L-galacto-hexopyranosylbenzene 3,7-(cyclic sulfate).The scope of this rearrangement was studied further on compounds with a 4-methoxybenzylidene instead of a benzylidene group, and a phenyl instead of a 2,4-dichlorophenyl group.In the latter reaction, in addition to 2-C-<(R)-acetoxy(phenyl)methyl>-3,4,5-tri-O-acetyl-2-deoxy-β-L-galacto-hexopyranosylbenzene, 1(S)-2-C-<(R)-acetoxy(phenyl)methyl>-1,3,4,5,6-penta-O-acetyl-2-deoxy-1-phenyl-L-gulitol was formed, the structure of which was established by X-ray analysis.