(+)-Halenaquinol dimethyl ether | 99463-22-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: (+)-Halenaquinol dimethyl ether
• 英文别名: halenaquinol dimethyl ether；(12bS)-(+)-8,11-dimethoxy-12b-methyl-1H-benzo[6,7]phenanthro(10,1-bc)furan-3,6(2H,12b H)-dione；(1S)-5,8-dimethoxy-1-methyl-14-oxapentacyclo[11.6.1.02,11.04,9.016,20]icosa-2,4,6,8,10,13(20),15-heptaene-12,17-dione
• CAS: 99463-22-6
• 化学式: C₂₂H₁₈O₅
• 分子量: 362.382
• InChiKey: HJGVPGQUGOEPRF-QFIPXVFZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  65.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (+)-Halenaquinol dimethyl ether 在 sodium dithionite 、 ammonium cerium(IV) nitrate 作用下， 以 甲醇 、 水 、 丙酮 为溶剂， 生成 halenaquinol
  参考文献：
  名称：

  Catalytic Asymmetric Synthesis of Halenaquinone and Halenaquinol

  摘要：

  DOI：

  10.1021/jo960773z
• 作为产物：
  描述：

  (1S,2S,4aS,8aR)-(-)-1,2,3,4,4a,7,8,8a-octahydro-1-(hydroxymethyl)-4a-methyl-2-naphthalenol 在 吡啶 、 3,5-二甲基吡唑 、 chromium(VI) oxide 、 potassium tert-butylate 、 氧气 、 对甲苯磺酸 、 溶剂黄146 、 三乙胺 、 N,N'-二环己基碳二亚胺 、 三氟乙酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 叔丁醇 作用下， 以 二氯甲烷 、 二甲基亚砜 、 苯 为溶剂， 反应 54.5h， 生成 (+)-Halenaquinol dimethyl ether
  参考文献：
  名称：

  Total synthesis of (+)-halenaquinol and (+)-halenaquinone. Experimental proof of their absolute stereostructures theoretically determined

  摘要：

  DOI：

  10.1021/ja00233a026

文献信息

• Absolute stereostructures of halenaquinol and halenaquinol sulfate, pentacyclic hydroquinones from the okinawan marine sponge xestospongia sapra, as determined by theoretical calculation of CD spectra
  作者：Motomasa Kobayashi、Nobuyoshi Shimizu、Isao Kitagawa、Yoshimasa Kyogoku、Nobuyuki Harada、Hisashi Uda

  DOI：10.1016/s0040-4039(00)89263-1

  日期：——

  The absolute stereostructures of two pentacyclic hydroquinones, halenaguinol () and halenaquinol sulfate () from the Okinawan marine sponge Xestospongia sapra, have been determined by means of theoretical calculation of CD spectra.

  通过CD光谱的理论计算，确定了来自冲绳海洋海绵Xestospongia sapra的两个五环对苯二酚，对苯二酚和硫酸对苯二酚的绝对立体结构。
• Novel Relationship between the Antifungal Activity and Cytotoxicity of Marine-Derived Metabolite Xestoquinone and Its Family
  作者：Mitsuhiro NAKAMURA、Takahiko KAKUDA、Jianhua QI、Masayuki HIRATA、Tomoaki SHINTANI、Yukio YOSHIOKA、Tetsuji OKAMOTO、Yuichi OBA、Hideshi NAKAMURA、Makoto OJIKA

  DOI：10.1271/bbb.69.1749

  日期：2005.1

  Xestoquinone and related metabolites (the xestoquinone family) occur in marine sponges and are known to show a variety of biological activities. In this study, the first comprehensive evaluation of antifungal activity was performed for xestoquinone and nine natural and unnatural analogues in comparison with their cytotoxicity. The cytotoxicity against two human squamous cell carcinoma cell lines, A431 and Nakata, indicated that the terminal quinone structure of the polycyclic molecules was important (xestoquinone, etc.) and that the presence of a ketone group at C-3 of the opposite terminus dramatically diminished the activity (halenaquinone, etc.). In contrast, a ketone group at C-3 enhanced the antifungal activity against the plant pathogen, Phytophthora capsici, regardless of the presence of a quinone moiety. The cytotoxicity and antifungal activity of the xestoquinone family were negatively correlated with each other.

  酮醌和相关代谢物（酮醌家族）存在于海绵中，并且已知表现出多种生物活性。在这项研究中，首次对酮醌和九种天然和非天然类似物的抗真菌活性与其细胞毒性进行了综合评估。对两种人鳞状细胞癌细胞系 A431 和 Nakata 的细胞毒性表明，多环分子的末端醌结构很重要（苯醌等），并且在相对末端的 C-3 处存在酮基团显着降低活性（海萘醌等）。相比之下，无论是否存在醌部分，C-3 处的酮基都会增强针对植物病原体辣椒疫霉的抗真菌活性。酮醌家族的细胞毒性和抗真菌活性彼此呈负相关。
• Total Synthesis, Absolute Configuration, and Later Isolation of (-)-Prehalenaquinone, a Putative Biosynthetic Precursor to the Marine Natural Products: Halenaquinone and Xestoquinone
  作者：Nobuyuki Harada、Tatsuo Sugioka、Hisashi Uda、Takeo Kuriki、Motomasa Kobayashi、Isao Kitagawa

  DOI：10.1021/jo00101a019

  日期：1994.11

  As part of the total syntheses of halenaquinone (1) and xestoquinone (4), cardiotonic and cytotoxic marine natural products isolated from tropical marine sponges, we have found a new reaction pathway of the DMSO/DCC/PPTS or PTFA reagent that is useful for constructing a dihydrofuran ring system. By application of the reaction, we prepared synthetic intermediate (3S,3aS,12bS)-(-)-8 with a dihydrofuran ring moiety, from which both (+)-halenaquinone (1) and (+)-xestoquinone (4) were synthesized; DMSO/DCC/PPTS oxidation of dihydrofuran-alcohol 8 led to 1, while acid-catalyzed dehydration led to 4. The mechanism of the new DMSO/DCC/PPTS or PTFA reaction was clarified by use of O-18 labeling. We postulated that these synthetic routes might simulate the biosyntheses of 1 and 4 in marine sponges, and putative biosynthetic precursor (3S,3aS,12bS)-(-)-7, named prehalenaquinone, was synthesized. Later, we succeeded in isolating (-)-7 from an Okinawan marine sponge, Xestospongia sapra.
• Synthesis of biotinylated xestoquinone that retains inhibitory activity against Ca2+ ATPase of skeletal muscle myosin
  作者：Mitsuhiro Nakamura、Takahiko Kakuda、Yuichi Oba、Makoto Ojika、Hideshi Nakamura

  DOI：10.1016/s0968-0896(03)00276-1

  日期：2003.7

  Xestoquinone isolated from a marine sponge binds to skeletal muscle myosin and inhibits its Ca2+ ATPase activity. In this study, we first examined xestoquinone and its analogues to assess the relationships between structure and myosin Ca2+ ATPase inhibitory activity. On the basis of the resultant data, we then designed a biotinylated xestoquinone analogue. Xestoquinone and its analogues were derived from extracts of the marine sponge Xestospongia sapra. Four xestoquinone analogues with a quinone structure significantly inhibited Ca2+ ATPase activity. In contrast, four xestoquinone analogues in which the quinone structure was converted to a quinol dimethyl ether did not inhibit Ca2+ ATPase activity. This suggests that the quinone moiety is essential for inhibitory activity. Then, we synthesized a biotinylated xestoquinone in which a biotin tag was introduced to a site far from the quinone moiety, and this molecule exhibited stronger inhibitory activity than that of xestoquinone. This biotinylated xestoquinone could be useful as a probe in studies of the xestoquinone-myosin binding mode. (C) 2003 Elsevier Science Ltd. All rights reserved.
• A Short Synthesis of (±)-Halenaquinone
  作者：Hamish S. Sutherland、Fabio E. S. Souza、Russell G. A. Rodrigo

  DOI：10.1021/jo010112o

  日期：2001.5.1