(1S,2S,7R,9R)-5-methyl-10,12-dioxatricyclo[7.2.1.0^2,7]dodec-4-en-8-one | 184677-22-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: (1S,2S,7R,9R)-5-methyl-10,12-dioxatricyclo[7.2.1.0^2,7]dodec-4-en-8-one
• 英文别名: levoglucosenone-isoprene adduct；(1S,2S,7R,9R)-5-methyl-10,12-dioxatricyclo[7.2.1.02,7]dodec-4-en-8-one
• CAS: 184677-22-3
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: HDBHANIRFZRXAB-YSSBGUOXSA-N

物化性质

• 沸点：
  315.3±42.0 °C(Predicted)
• 密度：
  1.178±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,2S,7R,9R)-5-methyl-10,12-dioxatricyclo[7.2.1.0^2,7]dodec-4-en-8-one 在 双氧水 、 sodium methylate 、 溶剂黄146 作用下， 以 甲醇 、 水 为溶剂， 反应 1.0h， 生成 (1R,6S,7S)-7-hydroxymethyl-3-methyl-8-oxabicyclo[4.3.0]non-3-en-9-one
  参考文献：
  名称：

  Valeev; Gaisina; Sagitdinova, Russian Journal of Organic Chemistry, 1996, vol. 32, # 9, p. 1319 - 1324

  摘要：

  DOI：
• 作为产物：
  描述：

  左旋葡萄糖酮 、 天然橡胶 在 zinc(II) chloride 作用下， 以 二氯甲烷 为溶剂， 以75%的产率得到(1S,2S,7R,9R)-5-methyl-10,12-dioxatricyclo[7.2.1.0^2,7]dodec-4-en-8-one
  参考文献：
  名称：

  Valeev; Gaisina; Sagitdinova, Russian Journal of Organic Chemistry, 1996, vol. 32, # 9, p. 1319 - 1324

  摘要：

  DOI：

文献信息

• Understanding reactivity and regioselectivity in Diels–Alder reactions of a sugar-derived dienophile bearing two competing EWGs. An experimental and computational study
  作者：Germán F. Giri、Ariel M. Sarotti、Rolando A. Spanevello

  DOI：10.1016/j.carres.2015.07.017

  日期：2015.10

  The effect of an extra EWG in the reactivity and regioselectivity in Diels-Alder reactions of beta-cyanolevoglucosenone and 4 different dienes was studied by a joint computational and experimental study. Conceptual DFT analysis successfully predicted an important enhancement in the reactivity, and correctly anticipated the regioselectivity in the reactions with isoprene. However, this static treatment

  通过联合计算和实验研究，研究了额外的EWG对β-氰基烯丙基葡糖醛酮和4种不同二烯的Diels-Alder反应的反应性和区域选择性的影响。DFT概念分析成功地预测了反应性的重要提高，并正确预测了与异戊二烯反应的区域选择性。然而，当处理涉及取代的蒽作为二烯的反应的区域化学偏好时，该静态处理失败。MPW1K / 6-31G *计算正确地再现了实验观察结果。基于收集的数据，我们发现，当处理没有清晰电子激活位置的二烯和亲二烯体时，相互作用原子的锥体化程度决定了DA反应的区域选择性。
• Assessing the halogen effect in Diels–Alder reactions involving chiral α-halo enones. A combined experimental and DFT computational approach
  作者：Ariel M. Sarotti、Rolando A. Spanevello、Alejandra G. Suárez

  DOI：10.1016/j.tetlet.2011.05.143

  日期：2011.8

  experimental and computational study was conducted to assess the effect of chlorine and bromine substitution in Diels–Alder reactions involving chiral α-halo enones as dienophiles. An important rate enhancement was observed in the case of acyclic dienes, while the use of cyclic dienes resulted in prolonged reaction times and lower yields. DFT calculations suggest that these reactions are governed by finely

  进行了一项实验和计算研究，以评估氯和溴取代在涉及手性α-卤代烯酮作为亲二烯体的Diels-Alder反应中的作用。在无环二烯的情况下观察到重要的速率提高，而使用环二烯导致延长的反应时间和较低的产率。DFT计算表明，这些反应受TS处几何和电子特征的精细平衡支配。
• Unusual regioselectivity in a Diels-Alder reaction of isoprene with levoglucosenone
  作者：M. S. Miftakhov、I. N. Gaisina、F. A. Valeev

  DOI：10.1007/bf01457782

  日期：1996.8

  The ZnCl2-catalyzed [4+2]-cycloaddition of isoprene with levoglucosenone is highly regio- and stereoselective.

  ZnCl2 催化的异戊二烯与左旋葡萄糖酮的 [4+2]-环加成反应具有高度的区域选择性和立体选择性。
• DFT calculations induced a regiochemical outcome revision of the Diels–Alder reaction between levoglucosenone and isoprene
  作者：Ariel M. Sarotti、Alejandra G. Suárez、Rolando A. Spanevello

  DOI：10.1016/j.tetlet.2011.04.021

  日期：2011.6

  An appealing inversion in the regiochemical outcome of Diels–Alder reactions between levoglucosenone (1) and its α-bromo derivative (5) with isoprene (2) was studied computationally. Based on different DFT calculations we concluded that both reactions should display the same regioselectivity. This result was further validated experimentally.

  通过计算研究了左旋葡糖酮（1）和其α-溴衍生物（5）与异戊二烯（2）之间的Diels-Alder反应的区域化学结果的反演。基于不同的DFT计算，我们得出结论，两个反应均应显示相同的区域选择性。该结果在实验上得到了进一步验证。
• Reactions of stereocontrolled intramolecular carbocyclization of levoglucosenone adduct with isoprene
  作者：B. T. Sharipov、O. Yu. Krasnoslobodtseva、L. V. Spirikhin、F. A. Valeev

  DOI：10.1134/s1070428010020144

  日期：2010.2

  An intramolecular carbocyclization was found of levoglucosenone adduct with isoprene providing a fused cyclobutane. The intramolecular oxacyclization of the adduct was performed under the treatment with I(2), H(3)PO(4), SOCl(2), and Pd/C leading to 1,4-epoxide. Methods were developed of radical and anionic (by Ferrier method) transformation of the adduct into chiral trans- and cis-decalins.