18 不斉合成による(+)-Mesembrineの合成

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概要

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• The asymmetric synthesis of 4,4-disubstituted 2-cyclohexenone (V) by the alkylation of the aldehyde enamine (III), from disubstituted acetaldehyde (I) and L-proline pyrrolidide (II), with methyl vinyl ketone, was stutied. It was shown that every cyclohexenone (V) obtained was optically active and the absolute configuration could be determined. The method was successfully applied to the total synthesis of (+)-mesembrine. By this asymmetric synthesis with the aldehyde (Ih), was obtained (+)-cyclohexenone (VI), whose absolute configuration was clearly shown to structure (VI) by ORD. The transformation of the (+)-cyclohexenone (VI) to partially optically active (+)-mesembrine was proceeded easily with ethanolic hydrochloric acid in 70% yield. The repeated recrystallization of partially optically active (+)-mesembrine hydrochloride resulted to obtain the practically optically pure (+)-mesembrine hydrochloride. Thus obtained synthetic (+)-mesembrine has antipodal optical property compaired to the natural (-)-mesembrine. Since the absolute configuration of synthetic (+)-mesembrine is to be represented by the structure (VII), it leads to an assingment of the absolute configuration of natural mesembrine that is represented by the structure (VIII).

• 天然有機化合物討論会の論文
• 1970-10-01

著者

• 山田 俊一

  Faculty of Pharmaceutical Sciences, University of Tokyo

• 山田 俊一

  Faculty Of Pharmaceutical Sciences University Of Tokyo

• 山田 俊一

  東京大学薬学部

• 大谷 元治

  興和(株)東京研究所

• 大谷 元治

  Tokyo Research Laboratories Kowa Company Ltd.

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• 18 不斉合成による(+)-Mesembrineの合成
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