Elucidation of the Racemization Mechanism of the α-Hydroxy Ketone Moiety (C_9-Position) of Optically Active Anthracyclinone Derivatives

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概要

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• In order to discriminate the possible racemization mechanisms shown in Chart 1 (for (S)-(-)-1a) for the α-hydroxy ketone moiety (C_9-position of the optically active anthracyclinones ((S)-(+)-1a-c), some plausible intermediates ((±)-2 and -3) and their equivalent ((R)-(-)-12) were first synthesized. Thus, the tertiary alcohol ((R)-(-)-12) was prepared from the 1'(S), 2 (R)-diol ((-)-10) according to the reaction scheme shown in Chart 2. The isomeric seven-membered α-hydroxy ketones ((±)-2 and -3) were elaborated from the 1,4-dihydronaphthalene (13), following the synthetic scheme shown in Charts 3 and 4 based on Dieckmann condensation, dihydroxylation, regioselective enol acetate formation, and oxidation as key steps. By subjecting the plausible intermediates ((±)-2 and -3,5,and (R)-(-)-12) to the racemization conditions, the facile loss of optical integrity observed for (S)-(+)-1a-c was found to proceed through the ring-expanded seven-membered α-hydroxy ketones ((±)-2 and -3 for (S)-(+)-1a, which might be produced by equilibrium C (Chart 1).

• 公益社団法人日本薬学会の論文
• 1984-11-25

著者

• 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

• 田本 克己

  Faculty Of Pharmaceutical Sciences University Of Tokyo

• 田本 克巳

  Development Research Laboratories I Sumitomo Pharmaceuticals Research Center

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