42 AlangiumアルカロイドAnkorineの構造と絶対配置 : (±)-Ankorineの全合成およびキナアルカロイドとの化学的相互関連
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概要
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Condensation of 2-benzyloxy-3,4-dimethoxyphenacyl bromide (V) with ethyl trans-3-ethyl-6-methoxy-2,3,4,5-tetrahydro-4-pyridineacetate (VII) gave lactam ketone VIII, which on sequential reduction with NaBH_4 and catalytic hydrogenolysis afforded lactam phenol XI. The benzyl ether of XI was cyclized with POCl_3 and the resulting quaternary salt [XIII (X=Cl)] was hydrogenated to furnish tricycle XV. The LiAlH_4 reduction of XV followed by hydrogenolysis provided racemic ankorine [(±)-IV]. A parallel synthetic route starting with lactim ether VII and 3,4,5-trimethoxyphenacyl bromide yielded tricycle XIX via lactam ketone IX. The 9,10,11-trimethoxy derivative (XIX) thus obtained did not correspond to the O-methyl derivative of natural ankorine. These results have identified the structure and relative stereochemistry of ankorine as IV. Ethyl cincholoiponate [(+)-XX], prepared from cinchonine (XXII), with V and K_2CO_3 in benzene yielded (-)-XXIII, which on sequential reduction with NaBH_4 and oxidation with Hg(OAc)_2-EDTA gave XXV and a compound presumed to be its isomer (XXVI). Hydrogenolysis of XXV followed by benzylation, alkaline hydrolysis, and thermal isomerization furnished a hardly separable 63: 37 mixture of the trans-(XXX) and the cis-acid (XXIX). The mixture was, after esterification, cyclized with POCl_3 to a mixture of trans- and cis-XXXII. Catalytic hydrogenation of the mixture of the quaternary salts (XXXII) and chromatographic purification of the basic product gave (-)-XV, which on LiAlH_4 reduction followed by hydrogenolysis furnished (-)-IV, identical with natural ankorine. Thus, the "synthetic incorporation of cincholoipon into ankorine" described above has proved that stereoformula IV is a complete expression for ankorine.
- 天然有機化合物討論会の論文
- 1975-10-01
著者
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吉藤 茂行
Faculty Of Pharmaceutical Sciences Of Hokuriku University
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藤井 澄三
金沢大・薬
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Yoshifuji Shigeyuki
Faculty Of Pharmaceutical Sciences Of Hokuriku University
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吉藤 茂行
金沢大・薬
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