37 抗腫瘍性海洋天然物(±)-Spiroxin Cの全合成(口頭発表の部)

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概要

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• Spiroxins A-E (1a-e), isolated from a marine-derived fungal strain LL37H248, have an unique bisnaphthospiroketal octacyclic ring system. Spiroxin A (1a), which is a major component produced from the culture medium, was reported to show not only antibacterial activity against Gram-positive and-negative bacteria, but also antitumor activity against ovarian carcinoma in nude mice, which was caused by its single-stranded DNA cleavage activity. However details of the mechanism are not clear. We report here the first total synthesis of (±)-spiroxin C (1c), in which a TBAF-actvated Suzuki-Miyaura cross-coupling reaction and an intramolecular bromoetherification reaction are included as key reactions. We planned that the basic spiroketal structure was constructed after fomation of a binaphthyl structure, which was expected to be obtained by a Pd(0)-catalyzed cross-coupling reaction (Scheme 1). Organoboronate (4) and enol triflate (5) were prepared from naphthol (6) and tetralone (7), respectively (Scheme 2). After several attempts, a key compound, binaphthyl (3), was found to be successfully obtained from these compounds by a TBAF-activated Suzuki-Miyaura cross-coupling reaction (Scheme 3). As shown in Scheme 4, the basic spiroketal structure of spiroxins was constructed via an intramolecular bromoetheration of 17 employing 2,4,4,6-tetrabromocyclohexa-2,5-dienone (18). Transformations involving a stereospecific epoxidation and a benzilic oxidation afforded spiroxin C.

• 2003-09-01

著者

• 今西 武

  大阪大学大学院薬学研究科

• 高橋 以都美

  Faculty Of Pharmaceutical Sciences Osaka University

• 坂井 孝行

  阪大院薬

• Imanishi Takeshi

  Graduate Shool Of Pharmaceutical Sciences Osaka University

• Imamura T

  Faculty Of Pharmaceutical Sciences Osaka University

• 宮下 和之

  阪大院薬

• 今西 武

  阪大院薬

• 宮下 和之

  大阪大学大学院薬学研究科

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