((3aS,6S,6aS)-6-isopropenyl-2,2-dimethyl-6,6a-dihydro-3aH-cyclopenta[1,3]dioxol-4-yloxy)trimethylsilane | 1003569-98-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ((3aS,6S,6aS)-6-isopropenyl-2,2-dimethyl-6,6a-dihydro-3aH-cyclopenta[1,3]dioxol-4-yloxy)trimethylsilane
• 英文别名: [(3aS,6S,6aS)-2,2-dimethyl-6-prop-1-en-2-yl-6,6a-dihydro-3aH-cyclopenta[d][1,3]dioxol-4-yl]oxy-trimethylsilane
• CAS: 1003569-98-9
• 化学式: C₁₄H₂₄O₃Si
• 分子量: 268.428
• InChiKey: CRLDYUUFTRMYKI-WCFLWFBJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.45
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl (3S,4R)-3-(tert-butyldimethylsiloxy)-4-methyl-5-oxocyclopent-1-enecarboxylate 、 ((3aS,6S,6aS)-6-isopropenyl-2,2-dimethyl-6,6a-dihydro-3aH-cyclopenta[1,3]dioxol-4-yloxy)trimethylsilane 在 正丁基锂 、 zinc(II) chloride 、 copper diacetate 、 manganese triacetate 、 溶剂黄146 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 、 2,2,2-三氟乙醇 为溶剂， 反应 3.0h， 以509 mg的产率得到ethyl (1S,2R,3aR,5aS,5bS,8aS,9aS,9bR)-1-(tert-butyldimethylsiloxy)-2,7,7-trimethyl-5-methylene-3,9-dioxodecahydro-6,8-dioxacyclopenta[b]-as-indacene-3a-carboxylate
  参考文献：
  名称：

  Dramatic Solvent Effect on the Diastereoselectivity of Michael Addition:  Study toward the Synthesis of the ABC Ring System of Hexacyclinic Acid

  摘要：

  During our studies toward the synthesis of the ABC ring system of hexacyclinic acid, we have observed a dramatic influence of the solvent on both our key steps. The diastereoselectivity of the intermolecular Michael addition could be totally reversed by changing the polarity of the solvent, and trifluoroethanol was found to be the optimal solvent for the following Mn(III)-promoted radical cyclization.

  DOI：

  10.1021/ol702566c
• 作为产物：
  描述：

  三甲基氯硅烷 、 (3aS,6S,6aS)-6-isopropenyl-2,2-dimethyltetrahydrocyclopenta[1,3]dioxol-4-one 在 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以96%的产率得到((3aS,6S,6aS)-6-isopropenyl-2,2-dimethyl-6,6a-dihydro-3aH-cyclopenta[1,3]dioxol-4-yloxy)trimethylsilane
  参考文献：
  名称：

  Dramatic Solvent Effect on the Diastereoselectivity of Michael Addition:  Study toward the Synthesis of the ABC Ring System of Hexacyclinic Acid

  摘要：

  During our studies toward the synthesis of the ABC ring system of hexacyclinic acid, we have observed a dramatic influence of the solvent on both our key steps. The diastereoselectivity of the intermolecular Michael addition could be totally reversed by changing the polarity of the solvent, and trifluoroethanol was found to be the optimal solvent for the following Mn(III)-promoted radical cyclization.

  DOI：

  10.1021/ol702566c

文献信息

• Dramatic influence of ester steric hindrance on the diastereoselectivity of a Michael addition towards the synthesis of the ABC tricycle of hexacyclinic acid
  作者：Alexandre Audic、Raphaël Oriez、Joëlle Prunet

  DOI：10.1016/j.tet.2020.131843

  日期：2021.1

  During our studies toward the synthesis of the ABC ring system of hexacyclinic acid, we observed an unexpected influence of the steric bulk of the ester group of the Michael acceptor in a key conjugate addition. We propose an eight-membered ring transition state to explain the formation of the undesired diastereomer in the case of unhindered esters.

  在我们对六环环酸的ABC环系统合成的研究中，我们观察到了关键的共轭加成反应中迈克尔受体酯基空间位阻的意外影响。我们提出了八元环过渡态，以解释在无阻酯的情况下不希望有的非对映异构体的形成。