17 鎖状立体制御を基盤としたエリスロマイシンAの形式全合成(口頭発表の部)

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概要

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• The unique structure of erythromycin A has attracted the attention of many chemists and syntheses of erythronolide A, an aglycone of erythromycin A, and erythromycin A itself have been achieved already by more than five groups in recent years. In most of these synthses, the stereocontrol on the cyclic system has been adopted for the introduction of chiral centers in these acyclic systems. In our case, the synthesis of this antibiotic was challenged based on acyclic stereoselection. 2,3-syn-2-Methyl-3-hydroxyesters 1a,b were synthesized from optically active imide 9 in several steps including a stereoselective reduction of β-ketoimide 8 by Zn(BH_4)_2, and were converted into segments 4 (left half) and 18 (a part of right half), respectively. (Me_2PhSi)_2NLi promoted condensation of these segments gave a desired C8-α-methyl compound 19a. However, all attempts for removal of the unnecessary hydroxy group at C_7 was unsuccessful. Thus, hydrogenation of the enone 20, obtained by mesylation of C_7-OH group followed by base treatment was examined, and the desired C_8-α-methyl-ketone 21 was obtained with unexpectedly high stereoselectivity. The compound 21 was successfully converted into the aldehyde 23b. Since erythromycin A has been derived from 23b by Woodward et al., the present work constitutes a formal total synthesis of erythromycin A. Aldehyde 5 corresponding to a right half segment (C_1-C_7) was also synthesized. Starting from 4a and 5, synthesis of the seco-acid derivative 28 involving all chiral centers necessary for erythronolide A synthesis is now in progress.

• 天然有機化合物討論会の論文
• 1987-07-25

著者

• 中田 忠

  理研

• 大石 武

  理研

• 大石 武

  Faculty Of Engineering Yokohama National University:(present Address)meiji College Of Pharmacy

• 大石 武

  理研:(現)明治薬科大学

• 中田 忠

  東京理大・理

• 福井 峰夫

  RIKEN (The Institute of Physical and Chemical Research)

• 福井 峰夫

  理研

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