64(PA2-4) 抗腫瘍活性物質エリオラニンの合成研究(ポスター発表の部)

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概要

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• Eriolanin(1) and Eriolangin(2) are novel antileukemic 1,10-secoeudesmanolides which were isolated from Eriophyllum lanatum Forbes by Kupchan and co-workers during a search for tumor-inhibitory natural produts from plant sources. Of much greater intereast to the synthetic chemist is the stereochemistry of (1) and (2) which consists of three configuous chiral centers within a cyclohexene ring along with an additional chiral center allylic and exocyclic to the ring. The total synthesis of these natural products has been disclosed by two laboratories. Herein, we report a novel synthesis of racemic eriolanin starting from (7). The C-4 chiral carbon of eriolanin was introduced by intramolecular iodo lactonization of (6). The introduction of the α-oriented methyl group at C-4 involved methylation of the lactone (14) followed by a kinetic protonation of the corresponding enolate giving the α-oriented methyl lactone (5) in the desired sense (83: 17). The γ-butylolactone moiety was constructed in the following sequence. Addition of dichloroketen to (11) took place from the β face, procuding (17) in a stereo- and regiocontrolled manner. 1,2-Carbonyl transposition of the adduct followed by C-2 unit elongation and Baeyer-Villiger oxidation afforded (28). Finally, Schlessinger intermediate (3) was successfully obtained via the introduction of a double bond at C-2 using phenylselenenyl chloride as a key step.

• 天然有機化合物討論会の論文
• 1987-07-25

著者

• 伴 義雄

  北大・薬

• 柴崎 正勝

  Faculty Of Pharmaceutical Sciences Hokkaido University

• 若松 武

  Faculty Of Pharmaceutical Sciences Hokkaido University

• 伴 義雄

  東邦大・薬

• 伴 義雄

  Faculty Of Pharmaceutical Sciences Hokkaido University

• 若松 武

  北大・薬

• 宮地 伸英

  北大・薬

• 尾崎 文博

  北大・薬

• 柴崎 正勝

  北大・薬

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