7 ザルザニンCおよびその関連化合物の合成

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概要

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• Guaianolides are a rapidly expanding group of natural products, comprising to date ca. 200 varieties. Because of their high biological activities, their efficient syntheses are the synthetic challenge which has received much attention during the past few years. We envisioned a general synthetic approach to the guaianolides which consisted of the solvolytic rearragement of the appropriately functionalized eudesmanolides such as compounds (8) and (21), which were prepared from α-santonin in 13% and 20% yields, respectively. Solvolytic rearrangement of 8 gave a mixture of endo- and exocyclic olefins (9 and 10). The selective epoxidation of 9 in this mixture with 0.5 molar equivalent of m-CPBA gave 10 and stereoisomeric epoxides (11) and (12) in 40%, 22%, and 29% yields, respectively. The resulting exocyclic olefin (10) was converted into a diene (16) in 66% yield in 3 steps. The regioselective epoxidation of 16 gave a 4: 1 mixture of an α-epoxide (17) and the corresponding β-epoxide (18) in 58% yield. The treatment of this mixture with Al(iPrO)_3 in refluxing toluene gave an α-allyl alcohol (19) which was converted to C_3-epizaluzanin C (2) in 15% overall yield. The diene (16) has already been converted to estafiatin (1) by Greene et al. The solvolytic rearragement of (21) and successive hydrolysis of the resulting inseparable mixture of acetates (22, 23, and 24) gave a mixture of α-allyl alcohols (19, 25, and 26). The treatment of this mixture with acetic acid in the presence of triphenylphosphine and diethyl azodicarboxylate gave a mixture of β-acetates (27, 28, and 29). Phenylselenenylation and successive hydrolysis of the resulting diselenide (30) gave 32 in 26% yield. Oxidative syn-elimination of 32 gave zaluzanin C (3).

• 天然有機化合物討論会の論文
• 1982-09-10

著者

• 安東 政義

  東北大理

• 高瀬 嘉平

  Department of Chemistry, Faculty of Science, Tohoku University

• 安東 政義

  東北大・理

• 山岡 弘明

  東北大・理

• 高瀬 嘉平

  東北大・理

• 高瀬 嘉平

  Department Of Chemistry Faculty Of Science Tohoku University

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