(1S^*,4aS^*,8aR^*)-4a,5,6,7,8,8a-hexahydro-1-(methoxymethyl)-1-propyl-2(1H)-naphthalenone | 136763-95-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S^*,4aS^*,8aR^*)-4a,5,6,7,8,8a-hexahydro-1-(methoxymethyl)-1-propyl-2(1H)-naphthalenone
• CAS: 136763-95-6；136781-88-9
• 化学式: C₁₅H₂₄O₂
• 分子量: 236.354
• InChiKey: GOAYEKZKHSIMGY-IPYPFGDCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.36
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  环戊二烯 、 (1S^*,4aS^*,8aR^*)-4a,5,6,7,8,8a-hexahydro-1-(methoxymethyl)-1-propyl-2(1H)-naphthalenone 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以44%的产率得到
  参考文献：
  名称：

  Geometrical aspects of the activation of enones by titanium tetrachloride: Diels-Alder reactions

  摘要：

  DOI：

  10.1021/ja00023a071
• 作为产物：
  描述：

  4,4a,5,6,7,8-hexahydro-1-propyl-2(3H)-naphthalenone 、 氯甲基甲基醚 生成 (1R^*,4aS^*,8aR^*)-4a,5,6,7,8,8a-hexahydro-1-(methoxymethyl)-1-propyl-2(1H)-naphthalenone 、 (1S^*,4aS^*,8aR^*)-4a,5,6,7,8,8a-hexahydro-1-(methoxymethyl)-1-propyl-2(1H)-naphthalenone
  参考文献：
  名称：

  Geometrical aspects of the activation of enones by titanium tetrachloride: Diels-Alder reactions

  摘要：

  DOI：

  10.1021/ja00023a071

文献信息

• Synthesis and Characterization of In-Plane and Out-of-Plane Enone−Lewis Acid Complexes:  Implications for Diels−Alder Reactions¹
  作者：D. K. Singh、James B. Springer、Patricia A. Goodson、Robert C. Corcoran

  DOI：10.1021/jo9518112

  日期：1996.1.1

  In order to determine the reactive geometries of enone-TiCl4 complexes in Diels-Alder reactions compounds 1a . TiCl4 and 1b . TiCl4 were prepared. A crystal structure of 1a . TiCl4 confirmed that the titanium in this complex has the desired out;of-plane geometry, with a Ti-O=C-C dihedral angle of 57.6 degrees, a value remarkably similar to dihedral angles found in simple carbocyclic compounds. Difference NOE studies support a similar geometry in solution. The magnitudes of key H-1 and C-13 NMR chemical shift changes upon complex formation indicate that the out-of-plane TiCl4 in 1a . TiCl4 is a stronger Lewis acid than the in-plane TiCl4 of 1e . TiCl4. These results are further supported by the changes in carbonyl stretching frequencies upon complex formation, with a Delta nu(C-O) for 1a . TiCl4 which is 24 cm(-1) larger than that for 1e . TiCl4. Expectations of heightened reactivity for 1a . TiCl4 as compared to 1e . TiCl4 have been confirmed; the former complex undergoes Diels-Alder reactions with cyclopentadiene 15 times more rapidly than the latter, despite being disfavored on a thermodynamic basis. These results suggest that the commonly held assumption of an in-place reactive geometry for titanium-based Lewis acid-mediated Diels-Aider reactions may be in error.