58 マクロリドのキラル合成 : 4. メチノリドの全合成
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概要
- 論文の詳細を見る
A highly stereoselective synthesis of the chiral seco-acid derivative (45) for the synthesis of methynolide from D-glucose is reported. The synthesis of the C-9 to C-13 fragment (13) of methynolide seco-acid started with diacetone-glucose (4) and proceeded via the compound (7) as shown in Scheme 2. The p-methoxybenzylidene group seemed to be most suitable for the protection of 1,2-diol of (12) because of its ease of removal under mild acidic conditions required in a later stage. Thus, treatment of (12) with MPMME and DDQ (Scheme 8) gave the acetal (13a,b) with excellent stereoselectivity (39:1). We may say this new acetalization to be "kinetically controlled." The C-1 to C-8 fragment (42) (Scheme 14) of seco-acid was synthesized by the highly stereo-controlled hydrogenation of (36) (Scheme 12) followed by transformation to the ketophosphonate (40) (Scheme 13), which was then converted to the carboxylic acid (42) (Scheme 14). The two fragments (42) and (43) were then coupled under basic conditions to afford (44), which was hydrolyzed smoothly to the known seco-acid derivative (45) (Scheme 14). The proton NMR spectrum of this compound was in good agreement with that kindly provided by Professor Ireland of the seco-acid (45). As the seco-acid (45) has been converted into methynolide and methymycin by Masamune, our work presented here constitutes a formal total synthesis of this macrolide antibiotic.
- 天然有機化合物討論会の論文
- 1983-09-15
著者
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及川 裕二
Faculty Of Pharmaceutical Sciences Hokkaido University
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及川 裕二
北大薬
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米光 宰
北大薬
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米光 宰
北海道大学薬学部
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米光 宰
北大 薬
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