Stereochemical Studies. XLVII. Asymmetric Reduction of 2-Alkyl-1,3,4-cyclopentanetriones with Lithium Aluminum Hydride decomposed by optically Active β-Aminoalcohols. Syntheses of optically Active Allethrolone and Prostaglandin E_1

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概要

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• Asymmetric reduction of several kinds of 2-alkyl-1,3,4-cyclopentanetriones (1) by the use of lithium aluminum hydride (LAH) partially decomposed by optically active β-aminoalcohols (7), was studied. It was found that the reduction of 2-propyl derivative (1c) with LAH decomposed by 3.0 eq. of (-)-N-methylephedrine (7a), in THF at -70°for 3 hr, followed by acetylation, gave (R)(-)-4-acetoxy-2-propyl-1,3-cyclopentanedione ((R) (-)-3c), 58% e.e., in 42% yield. When the same reduction procedure was applied to 2-allyl derivative (1b), (R) (-)-4-acetoxy-2-allyl derivative ((R) (-)-3b), 55% e.e., was obtained in 48% yield. Recrystallization of (R)(-)-3b from ether could improve the optical purity up to 97% e.e. The absolute configuration and optical purity of (R) (-)-3b and (R) (-)-3c were established by the chemical correlation with (R) (-)-allethrolone ((R) (-)-5). When 2-(6-carbomethoxyhexyl)-1,3,4-cyclopentanetrione (1a) was treated by the exploited reduction condition, the corresponding (R) (+)-alcohol ((R) (+)-2a), 54±6% e.e., from which PGE_1 had been synthesized, was prepared in 58% yield.

• 公益社団法人日本薬学会の論文
• 1977-06-25

著者

• 山田 俊一

  Faculty of Pharmaceutical Sciences, University of Tokyo

• 山田 俊一

  Faculty Of Pharmaceutical Sciences University Of Tokyo

• 北本 六良

  Faculty of Pharmaceutical Sciences, University of Tokyo

• 寺島 孜郎

  Faculty of Pharmaceutical Sciences, University of Tokyo

• 寺島 孜郎

  (財)相模中央化学研究所

• 寺島 孜郎

  Faculty Of Pharmaceutical Sciences University Of Tokyo:(present Address)sagami Chemical Research Cen

• 亀尾 一弥

  Faculty of Pharmaceutical Sciences, University of Tokyo

• 亀尾 一弥

  Research Center Taisho Pharmaceutical Co. Ltd.

• 北本 六良

  Faculty Of Pharmaceutical Sciences University Of Tokyo

関連論文

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