(2S,3R,4aS,5aR,9aS,10aR)-2-methyldecahydro-1,8,10-trioxa-anthracen-3-ol | 560108-14-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,3R,4aS,5aR,9aS,10aR)-2-methyldecahydro-1,8,10-trioxa-anthracen-3-ol
• 英文别名: (2S,3R,4aS,8aS,9aR,10aR)-2-methyl-decahydro-1,8,10-trioxa-anthracen-3-ol；(2S,3R,4aS,8aS,9aR,10aR)-2-methyldecahydro-2H-1,8,10-trioxaanthracen-3-ol；(1R,3S,5R,6S,8R,10S)-6-methyl-2,7,11-trioxatricyclo[8.4.0.03,8]tetradecan-5-ol
• CAS: 560108-14-7
• 化学式: C₁₂H₂₀O₄
• 分子量: 228.288
• InChiKey: VYYCMEBKTJGUDZ-NDUODEIHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 (2S,3R,4aS,5aR,9aS,10aR)-2-methyldecahydro-1,8,10-trioxa-anthracen-3-ol 在 吡啶 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以4.3 mg的产率得到(2S,3R,4aS,8aS,9aR,10aR)-2-methyl-decahydro-1,8,10-trioxa-anthracen-3-yl acetate
  参考文献：
  名称：

  Ladder Polyether Synthesis via Epoxide-Opening Cascades Using a Disappearing Directing Group

  摘要：

  The combination of a trimethylsilyl group, a Brønsted base, a fluoride source, and a hydroxylic solvent enables the first construction of the tetrad of tetrahydropyran rings found in the majority of the ladder polyether natural products by way of a cascade of epoxide-opening events that emulates the final step of Nakanishi's proposed biosynthetic pathway. The trimethylsilyl group disappears during the course of the cascade, and thus these are the first epoxide ring-opening cascades that afford ladder polyether subunits containing no directing groups at the end of the cascade.

  DOI：

  10.1021/ja057973p
• 作为产物：
  描述：

  (2S,3R)-2-prop-2-ynyloxan-3-ol 在 edetate disodium 、 potassium carbonate Sodium tetraborate decahydrate 、 正丁基锂 、 Oxone 、 Shi's ketone 、 四甲基乙二胺 、 三氟化硼乙醚 、 四丁基氟化铵 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 122.49h， 生成 (2S,3R,4aS,5aR,9aS,10aR)-2-methyldecahydro-1,8,10-trioxa-anthracen-3-ol
  参考文献：
  名称：

  SiMe₃-Based Homologation−Epoxidation−Cyclization Strategy for Ladder THP Synthesis

  摘要：

  [GRAPHICS]A trimethylsilyl (SiMe3) group is the basis of a strategy that emulates the three fundamental proposed processes in ladder polyether biosynthesis: chain homologation, stereoselective epoxidation (>95% ee or >95:5 dr), and endo-selective, stereospecific (inversion) hydroxyepoxide cyclization (>95:5 endo:exo, >95% dr). A tris-THP was synthesized in 18 total operations from commercial materials using this approach.

  DOI：

  10.1021/ol0347040

文献信息

• Entropic factors provide unusual reactivity and selectivity in epoxide-opening reactions promoted by water
  作者：Jeffery A. Byers、Timothy F. Jamison

  DOI：10.1073/pnas.1311133110

  日期：2013.10.15

  facilitating proton transfer, doubly activating the substrate for reaction, and perhaps most remarkably, reorganizing the substrate into a reactive conformation that leads to the observed product. This approach serves as an outline for a general strategy of exploiting solvent-solute interactions to achieve unusual reactivity in chemical reactions. These findings may also have implications in the biosynthesis

  尽管在水中发生了无数选择性酶促反应，但化学家很少利用这种介质的独特性质来控制反应的选择性。在这里，我们报告了对水促进反应的详细机理研究，该反应对通常不受欢迎的产品显示出高选择性。结构和动力学数据的结合表明，底物和水之间的协同作用不仅抑制了不需要的途径，而且水通过稳定过渡态的电荷、促进质子转移、双重激活底物进行反应来促进所需的途径，也许最显着的是，将底物重组为导致观察到的产物的反应性构象。这种方法作为利用溶剂-溶质相互作用来实现化学反应中不寻常反应的一般策略的概述。这些发现也可能对梯形聚醚天然产物的生物合成产生影响，例如短杆菌毒素和雪卡毒素。
• Morten, Christopher J.; Jamison, Timothy F., Journal of the American Chemical Society, 2009, vol. 131, p. 6678 - 6679
  作者：Morten, Christopher J.、Jamison, Timothy F.

  DOI：——

  日期：——
• Evidence That Epoxide-Opening Cascades Promoted by Water Are Stepwise and Become Faster and More Selective After the First Cyclization
  作者：Christopher J. Morten、Jeffery A. Byers、Timothy F. Jamison

  DOI：10.1021/ja1088748

  日期：2011.2.16

  A detailed kinetic study of the endo-selective epoxide-opening cascade reaction of a diepoxy alcohol in neutral water was undertaken using (1)H NMR spectroscopy. The observation of monoepoxide intermediates resulting from initial endo and exo cyclization indicated that the cascade proceeds via a stepwise mechanism rather than through a concerted one. Independent synthesis and cyclization of these monoepoxide intermediates demonstrated that they are chemically and kinetically competent intermediates in the cascade. Analysis of each step of the reaction revealed H H that both the rate and regioselectivity of cyclization improve as the cascade reaction proceeds. In the second step, cyclization of an epoxy alcohol substrate templated by a fused diad of two tetrahydropyran rings proceeds with exceptionally high regioselectivity (endo:exo = 19:1), the highest we have measured in the opening of a simple trans-disubstituted epoxide. The origins of these observations are discussed.
• Ladder Polyether Synthesis via Epoxide-Opening Cascades Using a Disappearing Directing Group
  作者：Graham L. Simpson、Timothy P. Heffron、Estíbaliz Merino、Timothy F. Jamison

  DOI：10.1021/ja057973p

  日期：2006.2.1

  The combination of a trimethylsilyl group, a Brønsted base, a fluoride source, and a hydroxylic solvent enables the first construction of the tetrad of tetrahydropyran rings found in the majority of the ladder polyether natural products by way of a cascade of epoxide-opening events that emulates the final step of Nakanishi's proposed biosynthetic pathway. The trimethylsilyl group disappears during the course of the cascade, and thus these are the first epoxide ring-opening cascades that afford ladder polyether subunits containing no directing groups at the end of the cascade.
• Ladder Polyether Synthesis via Epoxide-Opening Cascades Directed by a Disappearing Trimethylsilyl Group
  作者：Timothy P. Heffron、Graham L. Simpson、Estibaliz Merino、Timothy F. Jamison

  DOI：10.1021/jo1002455

  日期：2010.4.16

  Epoxide-opening cascades offer the potential to construct complex polyether natural products expeditiously and in a manner that emulates the biogenesis proposed for these compounds. Herein we provide a full account of our development of a strategy that addresses several important challenges of such cascades. The centerpiece of the method is a trimethylsilyl (SiMe3) group that serves several purposes and leaves no trace of itself by the time the cascade has come to an end. The main function of the SiMe3 group is to dictate the regioselectivity of epoxide opening. This strategy is the only general method of effecting endo-selective cascades under basic conditions.