68 不斉酸化反応を用いるアントラサイクリン系抗生物質の短段階不斉合成(口頭発表の部)

概要

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Extremely high enantioface selection was achieved in cisdihydroxylation of olefins with osmium tetroxide using chiral diamine 1. Enantioface selection in this reaction is shown by the general presentation 4. Since both (+)- and (-)-1 are readily available in optically pure forms, this method allows the synthesis of both enantiomers of diols with predictable absolute configuration. This efficient synthetic method was effective in the enantioselective synthesis of aglycons of anticancer antibiotics anthracyclins. Asymmetric oxidation of 13 followed by silane reduction afforded 17 in 85% ee. Friedel-Crafts reaction followed by recrystallization afforded optically pure 18, which was then converted into 4-demethoxy-9-deacetyl-7-dehydroxy-9-hydroxymethyldaunomycinone (22). Oxidation product (23) of 14 was also converted into 25 through two steps in 82% ee. Friedel-Crafts reaction followed by recrystallization afforded optically pure 26, which was then converted into 4-demethoxydaunomycinone (27) with conventional method. This is the shortest-step approach to the asymmetric synthesis of anthracyclins.
天然有機化合物討論会の論文
1988-09-26