82 ロジウム錯体を用いる高選択的不斉環化反応とイリドミルメシン類合成への応用(ポスター発表の部)

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概要

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• The asymmetric synthesis of 3,4-disubstituted cyclopentanones (4) by the cyclization of the aldehyde (3) in the presence of Rh(I) complex with BINAP as ligand was studied. The cyclization reaction proceeded in highly stereocontrolled fashion. As shown in table 3 and 4, cationic Rh(I) complex was found to be excellent catalyst for the asymmetric cyclization. This selective asymmetric cyclization was successfully applied to the total synthesis of the ant defensive secretion, (+)-iridomyrmecin (5) and (-)-isoiridomyrmecin (6). The cyclization of 3, derived from (-)-limonene, to the optically active trans-3,4-disubstituted cyclopentanone (4) (>99%de) was accomplished easily by using Rh[(+)-BINAP]ClO_4 in 93% yield. Aldol condensation of the diketone (4) to the bicyclic ketone (mixture of 8 and 9) was attained by treatment with KHSO_4. The mixture was converted to the ethylenedioxy acetal (10). Hydroboration of the acetal (10) with BH_3, followed by treatment with NaOH-H_2O_2, afforded the 7α-alcohol (11). After removal of the protected carbonyl function in 11 and subsequent oxidation with RuO_2/NaIO_4, the bicyclic 2β-methyl ketone (15a) was obtained. Compound 15a was converted to the (+)-iridomyrmecin (5) via the ozonolysis of the trimethylsilyl ether (16a) and subsequent lactonization. (-)-Isoiridomyrmecin (6) was also obtained in a similar manner to that described (15a) from the epimeric isomer (15b).

• 天然有機化合物討論会の論文
• 1992-09-10

著者

• 酒井 浄

  Faculty of Pharmaceutical Sciences, Kyushu University

• 酒井 浄

  Faculty Of Pharmaceutical Sciences Kyushu University

• 呉 暁明

  九大薬

• 高橋 陽一

  九大薬

• 舟越 和久

  九大薬

• 田中 正一

  九大薬

• 酒井 浄

  九大薬

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