3-oxo-1,2,3,5,6,7,8,8a-octahydronaphthalen-2-yl acetate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-oxo-1,2,3,5,6,7,8,8a-octahydronaphthalen-2-yl acetate
• 化学式: C₁₂H₁₆O₃
• 分子量: 208.257
• InChiKey: RKTTVQNPIGCHGI-NUHJPDEHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.01
• 重原子数：
  15.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  3-oxo-1,2,3,5,6,7,8,8a-octahydronaphthalen-2-yl acetate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 0.5h， 以88%的产率得到(S)-1,2,3,5,6,7,8,8a-Octahydro-naphthalene-2,3-diol
  参考文献：
  名称：

  Modeling the Effect of Substitution on the Pb(OAc)₄ Mediated Oxidative Cleavage of Steroidal 1,2-Diols

  摘要：

  We comment on the effects of angular substitution on the outcome of a Pb(OAc)(4) (LTA) mediated heterodomino reaction, with selected bicyclic unsaturated 1,2-diols, which is considered to proceed through a series of transformations in a single vessel. The first two, oxidative and pericyclic, are followed by the key step, an electrophilic addition of LTA to the olefin, responsible for the course of the domino process. In this study, the electrophilic addition of LTA to the double bond has been modeled with B3LYP, where the 6-31G* basis set is used for C, 0, and H atoms and the LANL2DZ method is used for Pb. The modeling in the gaseous phase and in solution has revealed the concerted nature of the addition of LTA to the double bond of the intermediate. The fact that LTA adds from the same side as the substituent R, for R=H and from the opposite side when R=CH3 has been attributed to steric hindrance, which causes deformation of the olefinic intermediate.

  DOI：

  10.1021/jo0505627
• 作为产物：
  描述：

  (+)-4,4a,5,6,7,8-hexahydro-2(3H)-naphthalenone 、 lead(IV) tetraacetate 以 苯 为溶剂， 反应 72.0h， 以75%的产率得到3-oxo-1,2,3,5,6,7,8,8a-octahydronaphthalen-2-yl acetate
  参考文献：
  名称：

  Modeling the Effect of Substitution on the Pb(OAc)₄ Mediated Oxidative Cleavage of Steroidal 1,2-Diols

  摘要：

  We comment on the effects of angular substitution on the outcome of a Pb(OAc)(4) (LTA) mediated heterodomino reaction, with selected bicyclic unsaturated 1,2-diols, which is considered to proceed through a series of transformations in a single vessel. The first two, oxidative and pericyclic, are followed by the key step, an electrophilic addition of LTA to the olefin, responsible for the course of the domino process. In this study, the electrophilic addition of LTA to the double bond has been modeled with B3LYP, where the 6-31G* basis set is used for C, 0, and H atoms and the LANL2DZ method is used for Pb. The modeling in the gaseous phase and in solution has revealed the concerted nature of the addition of LTA to the double bond of the intermediate. The fact that LTA adds from the same side as the substituent R, for R=H and from the opposite side when R=CH3 has been attributed to steric hindrance, which causes deformation of the olefinic intermediate.

  DOI：

  10.1021/jo0505627

文献信息

• Modeling the Effect of Substitution on the Pb(OAc)₄ Mediated Oxidative Cleavage of Steroidal 1,2-Diols
  作者：C. Öztürk、K. Topal、V. Aviyente、Nurcan Ş. Tüzün、E. Sánchez Fernández、S. Arseniyadis

  DOI：10.1021/jo0505627

  日期：2005.9.1

  We comment on the effects of angular substitution on the outcome of a Pb(OAc)(4) (LTA) mediated heterodomino reaction, with selected bicyclic unsaturated 1,2-diols, which is considered to proceed through a series of transformations in a single vessel. The first two, oxidative and pericyclic, are followed by the key step, an electrophilic addition of LTA to the olefin, responsible for the course of the domino process. In this study, the electrophilic addition of LTA to the double bond has been modeled with B3LYP, where the 6-31G* basis set is used for C, 0, and H atoms and the LANL2DZ method is used for Pb. The modeling in the gaseous phase and in solution has revealed the concerted nature of the addition of LTA to the double bond of the intermediate. The fact that LTA adds from the same side as the substituent R, for R=H and from the opposite side when R=CH3 has been attributed to steric hindrance, which causes deformation of the olefinic intermediate.