(1S,2R,4R,6R,7S,11S,12R,13S,16R,18R,19S,22R)-7,19-dihydroxy-11,22-dimethyl-5,10,17,21-tetraoxaheptacyclo[11.7.2.O^2,8.0^2,12.0^4,6.0^14,20.0^16,18]docosa-8,14(20)-diene-3,15-dione | 425371-21-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并吡喃类
• 英文名称: (1S,2R,4R,6R,7S,11S,12R,13S,16R,18R,19S,22R)-7,19-dihydroxy-11,22-dimethyl-5,10,17,21-tetraoxaheptacyclo[11.7.2.O^2,8.0^2,12.0^4,6.0^14,20.0^16,18]docosa-8,14(20)-diene-3,15-dione
• 英文别名: (+)-epoxyquinol A；epoxyquinol A；(1S,2R,4R,6R,7S,11S,12R,13S,16R,18R,19S,22R)-7,19-dihydroxy-11,22-dimethyl-5,10,17,21-tetraoxaheptacyclo[11.7.2.02,8.02,12.04,6.014,20.016,18]docosa-8,14(20)-diene-3,15-dione
• CAS: 425371-21-7
• 化学式: C₂₀H₂₀O₈
• 分子量: 388.374
• InChiKey: HJZHVRIBNUVKQX-YNQRKARISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.7
• 重原子数：
  28
• 可旋转键数：
  0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  118
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  O-苄基羟胺 、 (1S,2R,4R,6R,7S,11S,12R,13S,16R,18R,19S,22R)-7,19-dihydroxy-11,22-dimethyl-5,10,17,21-tetraoxaheptacyclo[11.7.2.O^2,8.0^2,12.0^4,6.0^14,20.0^16,18]docosa-8,14(20)-diene-3,15-dione 在 溶剂黄146 作用下， 以 乙酸乙酯 为溶剂， 反应 1.5h， 以100%的产率得到
  参考文献：
  名称：

  环氧喹诺尔A和相关分子的合成：探测环氧喹诺尔二聚体和2 H-吡喃前体的化学反应性

  摘要：

  使用2 H-吡喃环氧喹啉单体的[4 + 2]和[4 + 4]二聚作用，完成了环氧喹啉二聚体，环氧喹啉A，B和环氧双醇A（RKB-3564 D）的总合成。已经研究了2 H-吡喃前体的修饰，包括环氧醇的改变和二烯的立体化学。通过改变环氧喹诺2 H-吡喃核制备的稳定的2 H-吡喃在Diels-Alder环加成反应性亲二烯体中被评估为二烯。改善选择性保护2 H的[4 + 4]二聚化的广泛研究-吡喃单体可提供新型环氧醌类二聚体环氧双醇A，并获得了关于竞争性[4 + 2]和[4 + 4]二聚过程的宝贵见解。此外，已评估了环氧喹诺尔二聚体的化学反应性和结构修饰，包括[2 + 2]光环加成和[3,3]σ重排，表明有可能从二聚环氧醌类天然产物骨架中产生新的结构多样性。

  DOI：

  10.1021/jo050897o
• 作为产物：
  描述：

  (1R,5S,6S)-5-((tert-butyldimethylsilyl)oxy)-4-(((tert-butyldimethylsilyl)oxy)methyl)-7-oxabicyclo[4.1.0]hept-3-en-2-one 在 tris(dibenzylideneacetone)dipalladium (0) 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 三苯胂 、 溴 、 氧气 、 氟化氢吡啶 、 三乙胺 、 copper(l) chloride 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 10.0h， 生成 (1S,2R,4R,6R,7S,11S,12R,13S,16R,18R,19S,22R)-7,19-dihydroxy-11,22-dimethyl-5,10,17,21-tetraoxaheptacyclo[11.7.2.O^2,8.0^2,12.0^4,6.0^14,20.0^16,18]docosa-8,14(20)-diene-3,15-dione
  参考文献：
  名称：

  通过不对称的羟醛方法对它们的常见单体前体进行抗血管生成的五肽二聚体，环氧喹诺酚A和B的对映选择性全合成

  摘要：

  通过由Evans不对称醛醇缩合反应获得的单体戊二醛前体的氧化二聚反应和一系列操作简单的转化，实现了具有独特的戊二烯二聚结构和有效的抗血管生成活性的环氧喹诺尔A和B的新对映选择性全合成。

  DOI：

  10.1016/j.tetlet.2004.12.001

文献信息

• Total Synthesis of Epoxyquinols A, B, and C and Epoxytwinol A and the Reactivity of a 2<i>H</i>-Pyran Derivative as the Diene Component in the Diels−Alder Reaction
  作者：Mitsuru Shoji、Hiroki Imai、Makoto Mukaida、Ken Sakai、Hideaki Kakeya、Hiroyuki Osada、Yujiro Hayashi

  DOI：10.1021/jo048425h

  日期：2005.1.1

  the total synthesis of epoxyquinols A, B, and C and epoxytwinol A (RKB-3564D) are described. In the first-generation synthesis, the HfCl4-mediated diastereoselective Diels−Alder reaction of furan with Corey's chiral auxiliary has been developed. In the second-generation synthesis, a chromatography-free preparation of an iodolactone, by using acryloyl chloride as the dienophile in the Diels−Alder reaction

  描述了环氧喹啉A，B和C以及环氧双酚A（RKB-3564D）的全合成的两种形式的全部细节。在第一代合成中，HfCl 4介导的呋喃与科里的手性助剂的非对映选择性Diels-Alder反应已得到开发。在第二代合成中，开发了一种无色谱法制备碘代内酯的方法，该方法通过使用丙烯酰氯作为呋喃的Diels-Alder反应中的亲二烯体，并开发了由脂肪酶介导的环己烯醇衍生物的动力学拆分方法。第二代合成适合大规模制备。仿生级联反应涉及氧化，6π-电环化，然后Diels-Alder二聚化是环氧喹诺醇A，B和C的复杂七环结构形成的关键反应。 6π-电环化和正式的[4 + 4]环加成反应。2小时由氧化/6π-电环化生成的β-吡喃起良好的二烯作用，可与数个亲二烯体反应，一步生成多环化合物。氮杂五环化合物通过类似的级联反应合成，该级联反应由四个连续步骤组成：氧化，亚胺形成，6π-氮杂电子环化和Diels-Alder二聚化。
• Angiogenesis Inhibitor Epoxyquinol A:  Total Synthesis and Inhibition of Transcription Factor NF-κB
  作者：Chaomin Li、Sujata Bardhan、Emily A. Pace、Mei-Chih Liang、Thomas D. Gilmore、John A. Porco

  DOI：10.1021/ol026513n

  日期：2002.9.1

  [reaction: see text] The asymmetric synthesis of the natural product (+)-epoxyquinol A (1) and related epoxyquinoid dimers, employing a cascade oxidation/electrocyclization/Diels-Alder dimerization sequence, is reported. In addition, we show that 1 and related molecules inhibit activation of the transcription factor NF-kappaB.

  [反应：见正文]据报道，采用级联氧化/电环化/ Diels-Alder二聚化顺序，天然产物（+）-环氧喹啉A（1）和相关的环氧醌二聚体的不对称合成。此外，我们显示1和相关的分子抑制转录因子NF-κB的激活。
• Practical synthesis of ECH and epoxyquinols A and B from (−)-shikimic acid
  作者：Guiyin Luo、Yuanliang Jia、Yue Hu、Folei Wu、Maolin Wang、Xiaochuan Chen

  DOI：10.1039/d2ob00559j

  日期：——

  An efficient synthesis of ECH, epoxyquinols A and B, and two bioactive analogs EqM and RKTS-33 has been completed starting from (−)-shikimic acid. Rapid establishment of the desired epoxyquinol core is facilitated through a key allylic oxidation with high stereoselectivity, which is achieved by fine tuning the cyclohexene substrate structure and reaction conditions.

  从 (-)-莽草酸开始，已经完成了 ECH、环氧喹啉 A 和 B 以及两种生物活性类似物 EqM 和 RKTS-33 的有效合成。通过具有高立体选择性的关键烯丙基氧化促进所需环氧喹啉核的快速建立，这是通过微调环己烯底物结构和反应条件来实现的。
• Total synthesis of the novel angiogenesis inhibitors epoxyquinols A and B
  作者：Goverdhan Mehta、Kabirul Islam

  DOI：10.1016/s0040-4039(03)00621-x

  日期：2003.4

  The synthesis of the recently discovered angiogenesis inhibitors epoxyquinols A and B, having novel polyketide derived dimeric structures, has been accomplished from the readily available Diels-Alder adduct of cyclopentadiene and p-benzoquinone through a short, simple and flexible strategy that is diversity oriented and can be adapted to an asymmetric variant. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Different Reaction Modes for the Oxidative Dimerization of Epoxyquinols and Epoxyquinones. Importance of Intermolecular Hydrogen-Bonding
  作者：Mitsuru Shoji、Hiroki Imai、Isamu Shiina、Hideaki Kakeya、Hiroyuki Osada、Yujiro Hayashi

  DOI：10.1021/jo0355303

  日期：2004.3.1

  An oxidative dimerization reaction, involving the three successive steps of oxidation, 6pi-electrocyclization, and Diels-Alder reaction, has been experimentally and theoretically investigated for the three 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one derivatives epoxyquinol 3, epoxyquinone 6, and cyclohexenone 10. Of the sixteen possible modes of the oxidation/6pi-electrocylization/Diels-Alder reaction cascade for the epoxyquinone 6, and eight for the cyclohexenone 10, only the endo-anti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero modes are, respectively, observed, while both endo-anti(epoxide)-anti(Me)-hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with the epoxyquinol 3. Intermolecular hydrogen-bonding is found to be the key cause of formation of both epoxyquinols A and B with 3, although epoxyquinone 6 and cyclohexenone 10 both gave selectively only the epoxyquinol A-type product. In the dimerization of epoxyquinol 3, two monomer 2H-pyrans 5 interact with each other to afford intermediate complex 28 or 29 stabilized by hydrogen-bonding, from which Diels-Alder reaction proceeds. Theoretical calculations have also revealed the differences in the reaction profiles of epoxyquinone 6 and cyclohexenone 10. Namely, the rate-determining step of the former is the Diels-Alder reaction, while that of the latter is the 6pi-electrocyclization.