(2S,3R)-2-[[(2R,3R)-3-[[(2R,3R)-3-methyloxiran-2-yl]methyl]oxiran-2-yl]methyl]oxan-3-ol | 954111-09-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (2S,3R)-2-[[(2R,3R)-3-[[(2R,3R)-3-methyloxiran-2-yl]methyl]oxiran-2-yl]methyl]oxan-3-ol
• CAS: 954111-09-2
• 化学式: C₁₂H₂₀O₄
• 分子量: 228.288
• InChiKey: MXGTZTQDZGJTSB-ZZLGJBLRSA-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：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  54.5
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S,3R)-2-[[(2R,3R)-3-[[(2R,3R)-3-methyloxiran-2-yl]methyl]oxiran-2-yl]methyl]oxan-3-ol 在 水 、 silica gel 作用下， 以 二氯甲烷 为溶剂， 反应 75.0h， 生成 (2S,3R,5R)-5-[(2S,3aS,7aR)-3,3a,5,6,7,7a-hexahydro-2H-furo[3,2-b]pyran-2-yl]-2-methyloxolan-3-ol
  参考文献：
  名称：

  Evidence That Epoxide-Opening Cascades Promoted by Water Are Stepwise and Become Faster and More Selective After the First Cyclization

  摘要：

  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.

  DOI：

  10.1021/ja1088748
• 作为产物：
  描述：

  在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以99%的产率得到(2S,3R)-2-[[(2R,3R)-3-[[(2R,3R)-3-methyloxiran-2-yl]methyl]oxiran-2-yl]methyl]oxan-3-ol
  参考文献：
  名称：

  Morten, Christopher J.; Jamison, Timothy F., Journal of the American Chemical Society, 2009, vol. 131, p. 6678 - 6679

  摘要：

  DOI：

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.