[(1S,4aS)-2,2-dimethyl-3,4,4a,5,6,7-hexahydro-1H-naphthalen-1-yl]methanol | 1187954-10-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [(1S,4aS)-2,2-dimethyl-3,4,4a,5,6,7-hexahydro-1H-naphthalen-1-yl]methanol
• CAS: 1187954-10-4
• 化学式: C₁₃H₂₂O
• 分子量: 194.317
• InChiKey: CRLHTRNOOOAKJW-CMPLNLGQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  [(1S,4aS)-2,2-dimethyl-3,4,4a,5,6,7-hexahydro-1H-naphthalen-1-yl]methanol 、 二苯二硫醚 在 三丁基膦 作用下， 以 四氢呋喃 为溶剂， 反应 9.0h， 以75%的产率得到(5S,8aS)-6,6-dimethyl-5-(phenylsulfanylmethyl)-2,3,5,7,8,8a-hexahydro-1H-naphthalene
  参考文献：
  名称：

  Enantioselective Synthesis and Olfactory Evaluation of Bicyclic α- and γ-Ionone Derivatives: The 3D Arrangement of Key Molecular Features Relevant to the Violet Odor of Ionones

  摘要：

  Violet smelling ionones 1-3, occurring in the headspace of different flowers, are well-known perfumery raw materials. With the goal to recognize the still ill-defined spatial arrangement of structural features relevant to the binding of ionones to olfactory G-protein coupled receptors, through B3LYP/6-31G(d) modeling studies we identified bicyclic compounds 7-9 as conformationally constrained 13-alkyl-substituted analogues of monocyclic alpha- and gamma-ionones. They were thus synthesized to evaluate the olfactory properties. The enantioselective syntheses of 7-9 entailed two common key steps: (i) a Diels-Alder reaction to construct the octalinic core and (ii) a Julia-Lythgoe olefination to install the alpha,beta-enone side chain. The odor thresholds of synthetic 7 and 9 were significantly lower than the corresponding parent ionones, and 9 showed the lowest threshold value among violet-smelling odorants examined so far. Modeling studies Suggested a nearly identical spatial orientation of key hydrophobic and polar moieties of compounds 1, 3, and 4-9. Presumably, interaction of these moieties with ionone olfactory receptors (ORs) triggers a similar receptor code that is ultimately interpreted by the human brain as a pleasant woody-violet smell. These results open the way to studies aimed at identifying and modeling complementary binding sites on alpha-helical domains of ionone receptor proteins.

  DOI：

  10.1021/jo9014936
• 作为产物：
  描述：

  苯基乙烯基砜 、 [(S)-6,6-dimethyl-2-vinylcyclohex-2-enyl]methanol O-tert-butyldiphenylsilyl ether 在 对苯二酚 、 四丁基氟化铵 、 magnesium 作用下， 以 甲苯 、 四氢呋喃 、 甲醇 为溶剂， 反应 36.0h， 以37%的产率得到[(1S,4aS)-2,2-dimethyl-3,4,4a,5,6,7-hexahydro-1H-naphthalen-1-yl]methanol
  参考文献：
  名称：

  Enantioselective Synthesis and Olfactory Evaluation of Bicyclic α- and γ-Ionone Derivatives: The 3D Arrangement of Key Molecular Features Relevant to the Violet Odor of Ionones

  摘要：

  Violet smelling ionones 1-3, occurring in the headspace of different flowers, are well-known perfumery raw materials. With the goal to recognize the still ill-defined spatial arrangement of structural features relevant to the binding of ionones to olfactory G-protein coupled receptors, through B3LYP/6-31G(d) modeling studies we identified bicyclic compounds 7-9 as conformationally constrained 13-alkyl-substituted analogues of monocyclic alpha- and gamma-ionones. They were thus synthesized to evaluate the olfactory properties. The enantioselective syntheses of 7-9 entailed two common key steps: (i) a Diels-Alder reaction to construct the octalinic core and (ii) a Julia-Lythgoe olefination to install the alpha,beta-enone side chain. The odor thresholds of synthetic 7 and 9 were significantly lower than the corresponding parent ionones, and 9 showed the lowest threshold value among violet-smelling odorants examined so far. Modeling studies Suggested a nearly identical spatial orientation of key hydrophobic and polar moieties of compounds 1, 3, and 4-9. Presumably, interaction of these moieties with ionone olfactory receptors (ORs) triggers a similar receptor code that is ultimately interpreted by the human brain as a pleasant woody-violet smell. These results open the way to studies aimed at identifying and modeling complementary binding sites on alpha-helical domains of ionone receptor proteins.

  DOI：

  10.1021/jo9014936

文献信息

• Enantioselective Synthesis and Olfactory Evaluation of Bicyclic α- and γ-Ionone Derivatives: The 3D Arrangement of Key Molecular Features Relevant to the Violet Odor of Ionones
  作者：Marco Luparia、Laura Legnani、Alessio Porta、Giuseppe Zanoni、Lucio Toma、Giovanni Vidari

  DOI：10.1021/jo9014936

  日期：2009.9.18

  Violet smelling ionones 1-3, occurring in the headspace of different flowers, are well-known perfumery raw materials. With the goal to recognize the still ill-defined spatial arrangement of structural features relevant to the binding of ionones to olfactory G-protein coupled receptors, through B3LYP/6-31G(d) modeling studies we identified bicyclic compounds 7-9 as conformationally constrained 13-alkyl-substituted analogues of monocyclic alpha- and gamma-ionones. They were thus synthesized to evaluate the olfactory properties. The enantioselective syntheses of 7-9 entailed two common key steps: (i) a Diels-Alder reaction to construct the octalinic core and (ii) a Julia-Lythgoe olefination to install the alpha,beta-enone side chain. The odor thresholds of synthetic 7 and 9 were significantly lower than the corresponding parent ionones, and 9 showed the lowest threshold value among violet-smelling odorants examined so far. Modeling studies Suggested a nearly identical spatial orientation of key hydrophobic and polar moieties of compounds 1, 3, and 4-9. Presumably, interaction of these moieties with ionone olfactory receptors (ORs) triggers a similar receptor code that is ultimately interpreted by the human brain as a pleasant woody-violet smell. These results open the way to studies aimed at identifying and modeling complementary binding sites on alpha-helical domains of ionone receptor proteins.