Stereochemical Studies. XLI. Asymmetric Synthesis of optically Active 4a-Methyl-4,4a, 9,10-tetrahydro-2 (3H)-phenanthrone Derivatives, Key Intermediates for Total Syntheses of optically Active Diterpenes and Steroids

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概要

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• Exploitation of the synthetic route to optically active (R) (-)-4a-methyl-4,4a, 9,10-tetrahydro-2 (3H)-phenanthrone ((R) (-)-6a) and its 7-methoxy derivative ((R) (-)-6b) from optically active (R)-2-cyclohexenones ((R) (+)-1) or (S) (+)-δ-ketoaldehydes ((S) (+)-2) were attempted. (R) (+)-1 and (S) (+)-2 could be obtained by the asymmetric synthesis via the enamines prepared from L-proline-derived pyrrolidines ((S)-5) and dl-2-arylpropionaldehydes (dl-4). Base-catalysed cyclization of (S) (+)-2,followed by ketalization and Jones oxidation, gave (S) (-)-cyclohexanone ((S) (-)-7). The same compounds could be also prepared from (R) (+)-1 by successive epoxidation, ketalization, reduction, and Jones oxidation. Addition of N, N-dimethyl lithioacetamide 1,4-diazabicyclo [2,2,2] octane complex to (S) (-)-7,followed by reduction with Vitride and cyclization with polyphosphoric acid, afforded (R) (-)-6a, 85% optically pure, and (R) (-)-6b, [α]^20_D-223° (ethanol). Detailed studies on reaction products and conditions, and preliminary experiments with racemic compounds were also carried out.

• 公益社団法人日本薬学会の論文
• 1976-06-25

著者

• 山田 俊一

  Faculty of Pharmaceutical Sciences, University of Tokyo

• 山田 俊一

  Faculty Of Pharmaceutical Sciences University Of Tokyo

• 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

• 曽根 孝範

  Faculty of Pharmaceutical Sciences, University of Tokyo

• 曽根 孝範

  Life-science Institute, Asahi Chemical Industry Co., Ltd.

• 曽根 孝範

  Life-science Institute Asahi Chemical Industry Co. Ltd.

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