3,4-dehydroxestoquinol dimethyl ether | 183727-64-2

• 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: 3,4-dehydroxestoquinol dimethyl ether
• 英文别名: (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),15,17-octaen-12-one
• CAS: 183727-64-2
• 化学式: C₂₂H₁₈O₄
• 分子量: 346.383
• InChiKey: UZODPGBHMLFVDR-QFIPXVFZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  48.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,4-dehydroxestoquinol dimethyl ether 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 6.5h， 以100%的产率得到xestoquinol dimethyl ether
  参考文献：
  名称：

  使用不对称钯催化多烯环化全合成 (+)-Xestoquinone

  摘要：

  使用 (S)-(+)-BINAP 作为手性配体，通过钯 (0) 催化的三氟甲磺酸萘酯 44 的多烯环化反应以 68% ee 完成了 (+)-xestoquinone (1) 的首次全不对称合成。即使在银盐存在的情况下，使用相应的萘基溴 41 进行不对称多烯环化的尝试也给出了较差的对映选择性，因此举例说明了钯的配位状态对对映选择性的影响。还描述了一种在七元环醚前体上使用 [1,2]-Wittig 重排制备 6,7-二氢异苯并呋喃的新方法。

  DOI：

  10.1021/ja960807k
• 作为产物：
  描述：

  (+)-Halenaquinol dimethyl ether 在 cerium(III) chloride 、 对甲苯磺酸 作用下， 以 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 9.17h， 生成 3,4-dehydroxestoquinol dimethyl ether
  参考文献：
  名称：

  Synthesis of biotinylated xestoquinone that retains inhibitory activity against Ca2+ ATPase of skeletal muscle myosin

  摘要：

  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.

  DOI：

  10.1016/s0968-0896(03)00276-1

文献信息

• Silver salt effects on an asymmetric heck reaction. Catalytic asymmetric total synthesis of (+)-xestoquinone
  作者：Futoshi Miyazaki、Koichiro Uotsu、Masakatsu Shibasaki

  DOI：10.1016/s0040-4020(98)00797-2

  日期：1998.10

  An enantioselective total synthesis of (+)-xestoquinone has been achieved using a cascade-type asymmetric Heck reaction (in up to 63% ee and 39% chemical yield (66% conversion yield)) of the aryl bromide derivative (4). The use of a larger amount of silver exchanged zeolite resulted in a decrease in ee and yield. This is the first example of an effect of the amount of a silver salt on the ee and yield

  使用芳基溴化物衍生物（4）的级联型不对称Heck反应（高达ee的63％和化学收率的39％（转化率的66％））已经实现了对（+）-对甲苯醌的对映选择性全合成。使用大量的银交换沸石导致ee和产率降低。这是银盐量对ee和产品收率的影响的第一个例子。
• Further Developments of an Enantioselective Palladium-Catalyzed Polyene Cyclization: Surprising Solvent and Ligand Effects
  作者：Brian Keay、Daniela Lucciola

  DOI：10.1055/s-0030-1260785

  日期：2011.7

  The enantioselectivity of a Pd-catalyzed domino Heck-Mizoroki cyclization is dramatically enhanced by ligand and solvent choice. Electron-deficient ligands such as (R)-DIFLUOPPHOS gave 5 in %ee values ranging from 94% ee to >99% ee. EtOH was found to be superior to other solvents traditionally used in Heck-Mizoroki reactions, generally showing increases in enantioselectivity when compared to toluene

  配体和溶剂的选择显着提高了 Pd 催化的多米诺 Heck-Mizoroki 环化的对映选择性。缺电子配体如 (R)-DIFLOUPHOS 的 %ee 值为 5，范围从 94% ee 到 >99% ee。发现 EtOH 优于 Heck-Mizoroki 反应中传统使用的其他溶剂，与甲苯相比，通常表现出对映选择性的增加。还表明，微波加热可加速任一溶剂中的反应，并在不侵蚀 %ee 的情况下延长催化剂寿命。
• Total Synthesis of (+)-Xestoquinone Using an Asymmetric Palladium-Catalyzed Polyene Cyclization
  作者：Shawn P. Maddaford、Neil G. Andersen、Walter A. Cristofoli、Brian A. Keay

  DOI：10.1021/ja960807k

  日期：1996.1.1

  The first total asymmetric synthesis of (+)-xestoquinone (1) has been accomplished in 68% ee by a palladium(0)-catalyzed polyene cyclization of naphthyl triflate 44 using (S)-(+)-BINAP as the chiral ligand. Attempts at an asymmetric polyene cyclization using the corresponding naphthyl bromide 41 gave poor enantioselectivities even in the presence of silver salts, thus exemplifying the effect of the

  使用 (S)-(+)-BINAP 作为手性配体，通过钯 (0) 催化的三氟甲磺酸萘酯 44 的多烯环化反应以 68% ee 完成了 (+)-xestoquinone (1) 的首次全不对称合成。即使在银盐存在的情况下，使用相应的萘基溴 41 进行不对称多烯环化的尝试也给出了较差的对映选择性，因此举例说明了钯的配位状态对对映选择性的影响。还描述了一种在七元环醚前体上使用 [1,2]-Wittig 重排制备 6,7-二氢异苯并呋喃的新方法。
• 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.