[(S)-6,6-dimethyl-2-[2-(trimethylsilyl)-1-(phenylsulfonyl)ethyl]cyclohex-2-enyl]methanol O-tert-butyldiphenylsilyl ether | 1187954-09-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(S)-6,6-dimethyl-2-[2-(trimethylsilyl)-1-(phenylsulfonyl)ethyl]cyclohex-2-enyl]methanol O-tert-butyldiphenylsilyl ether
• 英文别名: [2-(benzenesulfonyl)-2-[(6S)-6-[[tert-butyl(diphenyl)silyl]oxymethyl]-5,5-dimethylcyclohexen-1-yl]ethyl]-trimethylsilane
• CAS: 1187954-09-1
• 化学式: C₃₆H₅₀O₃SSi₂
• 分子量: 619.028
• InChiKey: QEAJWNYYFFYBDR-BONSOQDYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.11
• 重原子数：
  42
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [(S)-6,6-dimethyl-2-[2-(trimethylsilyl)-1-(phenylsulfonyl)ethyl]cyclohex-2-enyl]methanol O-tert-butyldiphenylsilyl ether 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.67h， 以84%的产率得到[(S)-6,6-dimethyl-2-vinylcyclohex-2-enyl]methanol O-tert-butyldiphenylsilyl ether
  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：

  碘甲基三甲基硅烷 、 [(1S)-2-(benzenesulfonylmethyl)-6,6-dimethylcyclohex-2-en-1-yl]methoxy-tert-butyl-diphenylsilane 在 N,N-二甲基丙烯基脲 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.33h， 以86%的产率得到[(S)-6,6-dimethyl-2-[2-(trimethylsilyl)-1-(phenylsulfonyl)ethyl]cyclohex-2-enyl]methanol O-tert-butyldiphenylsilyl ether
  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