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。