[(1S)-2-(benzenesulfonylmethyl)-6,6-dimethylcyclohex-2-en-1-yl]methoxy-tert-butyl-diphenylsilane | 1187954-08-0

• 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: [(1S)-2-(benzenesulfonylmethyl)-6,6-dimethylcyclohex-2-en-1-yl]methoxy-tert-butyl-diphenylsilane
• CAS: 1187954-08-0
• 化学式: C₃₂H₄₀O₃SSi
• 分子量: 532.819
• InChiKey: IUEYVIINRXKRDU-SSEXGKCCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  37
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  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
• 作为产物：
  描述：

  [(S)-6,6-dimethyl-2-[(phenylsulfinyl)methyl]cyclohex-2-enyl]methanol O-tert-butyldiphenylsilyl ether 在 间氯过氧苯甲酸 作用下， 以 乙醚 为溶剂， 反应 0.33h， 以91%的产率得到[(1S)-2-(benzenesulfonylmethyl)-6,6-dimethylcyclohex-2-en-1-yl]methoxy-tert-butyl-diphenylsilane
  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

• A General and Concise Enantioselective Divergent Approach to 13-Alkyl-Substituted Ionones
  作者：Serena Bugoni、Valentina Merlini、Alessio Porta、Giuseppe Zanoni、Giovanni Vidari

  DOI：10.1002/cbdv.201400030

  日期：2014.10

  A novel enantioselective divergent route to 13‐alkyl derivatives of α‐ and γ‐ionone, important components of perfumes and fragrances, is reported. This relatively short and convenient methodology takes advantage of the use of a common intermediate, easily obtained from highly enantiomerically enriched (S)‐α‐ionone, which avoids the separate installation of the butenone side chain at C(6) for each analog

  报道了一种新的对映选择性发散路线，用于制备香水和香料的重要成分 α- 和 γ-紫罗兰酮的 13-烷基衍生物。这种相对简短和方便的方法利用了一种常见中间体的使用，该中间体很容易从高度对映异构体富集的 (S)-α-紫罗兰酮中获得，避免了在 C(6) 处为每个类似物单独安装丁烯酮侧链。合成化合物的嗅觉评估再次证实了 C(5) 处烷基取代基与嗅觉受体 (ORs) 在紫罗兰酮化学感受中的疏水相互作用的影响，并表明 C(13) 和侧链的共面取向更好几何拟合 OR 的腔。
• 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.