P-53 ジエン鉄カルボニル錯体を不斉発現素子とし用いた不斉合成反応の開発および生理活性物質の不斉合成(ポスター発表の部)

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概要

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• Recently, much attention has been directed to development of a useful tool for constructing a chiral center of acyclic carbon chains. In this session, we will present a novel method for 1,2-asymmetric induction of ketones and imines using diene (tricarbonyl)-iron complex as a chiral auxiliary and its application to asymmetric synthesis of (+)- and (-)-frontalin, hydroxyethylidene dipeptide isostere, and SS20846A. We succeeded in synthesizing both diastereomers 2 and 3 of the tertiary alcohols from Z-dienone complex 1 with a perfect stereoselectivity by simply changing organometallic reagents as a nucleophile. For application of this method, both enantiomers of 2-methyl-6-heptene-1,2-diol 9 and 12, which had been converted into (+)- and (-)-frontalin, were synthesized from the chiral Z-dienone complex 6. Nucleophilic addition of organocerium reagents to E-1-iminodiene complex 13 proceeded in highly diastereoselective manner to yield the secondary amine complexes 14 as a sole product. With an aim for synthesizing hydroxyethylidene isostere, we investigated the stereoselective introduction of β-hydroxy group into the amine complex 18. After numerous examinations, the reaction with I_2 in the presence of KI in CH_2Cl_2 gave rise to the desired trans oxazolidinone 20, regio and stereoselectively, which was converted into the aimed hydroxyethylidene peptide isostere in 6 steps. A LiClO_4 catalyzed cycloaddition of E-1-iminodiene complexes 23 with Danishefsky's diene proceeded in highly stereoselective manner to give 2-substituted dehydropiperidinone derivatives 24. The chiral cycloadduct 24a was converted into a biologically active piperidine alkaloid SS20846A in 3steps, by which its absolute configuration was revealed to be 2S, 4S.

• 天然有機化合物討論会の論文
• 1995-09-01

著者

• 竹本 佳司

  Faculty Of Pharmaceutical Sciences Osaka University

• 岩田 宙造

  阪大・薬

• 中本 貴久

  Faculty Of Pharmaceutical Sciences Osaka University

• 岩田 宙造

  阪大院薬

• 竹内 淳

  Faculty Of Pharmaceutical Sciences Osaka University

• Takemoto Yoshiji

  Faculty Of Pharmaceutical Sciences Osaka University

• Takemoto Y

  Graduate School Of Pharmaceutical Sciences Kyoto University

• 上田 茂生

  Faculty Of Pharmaceutical Sciences Osaka University

• 松井 栄樹

  阪大・薬

• 竹本 佳司

  阪大・薬

• 竹内 淳

  阪大・薬

• 上田 茂生

  阪大・薬

• 中本 貴久

  阪大・薬

• 森尾 健一郎

  阪大・薬

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