PHOTO-OXYGENATION OF POLYHYDROXYALKYLFURANS: REARRANGEMENT OF O-ACETYL DERIVATIVES

Article abstract of DOI:10.1016/S0008-6215(00)90391-4

The photo-oxygenation of ethyl 2-methyl-5-(1,2,3,4-tetra-O-acetyl-D-lyxo-tetritol-1-yl)-3-furoate, ethyl 2-methyl-5-(1,2,3,4-tetra-O-acetyl-D-arabino-tetritol-1-yl)-3-furoate, 3-acetyl-2-methyl-5-(1,2,3,4-tetra-O-acetyl-D-arabino-tetritol-1-yl)furan, and ethyl 5-(1,4-di-O-acetyl-2,3-O-isopropylidene-D-lyxo-tetritol-1-yl)-2-methyl-3-furoate yielded the corresponding 1,4-endo-peroxides (3a-3d as pairs of diastereomers).Each diastereomer of the pairs 3a and 3d was isolated by fractional crystallisation.The rearrangement of the endo peroxides at room temperature, by dissolution in CDCl3, yielded the corresponding diepoxides and monoepoxides.The reduction of 3a-3d with methyl sulphide yielded the corresponding γ-diketones, ethyl (E)-2-C-acetyl-5,6,7,8-tetra-O-acetyl-2,3-dideoxy-D-lyxo-oct-2-en-4-ulosonate, ethyl (E)-2-C-acetyl-5,6,7,8-tetra-O-acetyl-2,3-dideoxy-D-arabino-oct-2-en-4-ulosonte, 3-C-acetyl-6,7,8,9-tetra-O-acetyl-1,3,4-trideoxy-D-arabino-non-3-eno-2,5-diulose, and ethyl (E)-2-C-acetyl-5,8-di-O-acetyl-2,3-dideoxy-6,7-O-isopropylidene-D-lyxo-oct-2-en-4-ulosonate, which can isomerise into the correspodig Z isomers.