K. Tadano, H. Kimura, M. Hoshino
Oct 1, 1987
Citations
0
Influential Citations
9
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
The known 3-O-benzyl-D-xylose was converted into methyl (4R,5R,6R)-4,6,7-triacetoxy-5-benzyloxy-2-(methoxycarbonyl)heptanoate (8) by employing Knoevenagel condensation of 2,4,5-tri-O-acetyl-3-O-benzyl-aldehydo-D-xylose with dimethyl malonate as a key reaction. O-Deacetylation of 8 and successive glycol cleavage followed by acetylation gave a mixture of (1S,4R,5R,6R)-5-acetoxy-6-benzyloxy-4-methoxycarbonyl-2-oxobicyclo[2.2.1]heptan-3-one and dimethyl (2R,3R,4S)-2,4-diacetoxy-3-benzyloxy-1,1-cyclopentanedicarboxylate (12), which was converted into 12 exclusively. This enantiomerically pure highly oxygenated cyclopentane dicarboxylate 12 was converted into (3S,4S)-3-benzyloxy-1-(t-butyldiphenylsilyloxymethyl)-4-hydroxy-1-cyclopentene (15) by 1) thermal demethoxycarbonylation accompanied by β-elimination of the acetoxyl group, 2) diisobutylaluminium hydride reduction, and 3) selective protection of thus formed 1-cyclopentene-1-methanol. Pyridinium chlorochromate oxidation of 15 followed by reduction with sodi...