(1R,2S,4R)-1-methyl-4-(1-oxoethyl)cyclohexane 1,2-oxide | 57072-60-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: (1R,2S,4R)-1-methyl-4-(1-oxoethyl)cyclohexane 1,2-oxide
• 英文别名: Ethanone, 1-(6-methyl-7-oxabicyclo[4.1.0]hept-3-yl)-, (1alpha,3alpha,6alpha)-(9CI)；1-[(1S,3R,6R)-6-methyl-7-oxabicyclo[4.1.0]heptan-3-yl]ethanone
• CAS: 57072-60-3
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: VPQYGKRHSKLXJB-HRDYMLBCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  29.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2S,4R)-1-methyl-4-(1-oxoethyl)cyclohexane 1,2-oxide 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 60.0h， 生成 (1R,2S,4R)-1-methyl-4-acetoxycyclohexane 1,2-oxide
  参考文献：
  名称：

  Trichodiene synthase. Synergistic inhibition by inorganic pyrophosphate and aza analogs of the bisabolyl cation.

  摘要：

  A series of aza analogs of the bisabolyl and alpha-terpinyl cations were tested as inhibitors of the sesquiterpene cyclase, trichodiene synthase. Both (R)- and (S)-16 and (R)- and (S)-13 as well as trimethylamine were only weak inhibitors when incubated alone. In the presence of inorganic pyrophosphate, itself a known competitive inhibitor of trichodiene synthase, all five amines showed strong cooperative competitive inhibition with an enhancement factor estimated to be 10-40. The apparent induced inhibition constant alpha-K(j) decreased in going from trimethylamine to the monoterpene analogs 13 and was strongest for the sesquiterpene analogs 16, indicating that both electrostatic and hydrophobic interactions are important in the binding of each intermediate analog. The cyclase showed little discrimination, however, between the individual enantiomers of each inhibitor.

  DOI：

  10.1021/jo00038a040
• 作为产物：
  描述：

  甜橙提取物 在 二甲基硫 、 碳酸氢钠 、 臭氧 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 4.5h， 生成 (1R,2S,4R)-1-methyl-4-(1-oxoethyl)cyclohexane 1,2-oxide
  参考文献：
  名称：

  Trichodiene synthase. Synergistic inhibition by inorganic pyrophosphate and aza analogs of the bisabolyl cation.

  摘要：

  A series of aza analogs of the bisabolyl and alpha-terpinyl cations were tested as inhibitors of the sesquiterpene cyclase, trichodiene synthase. Both (R)- and (S)-16 and (R)- and (S)-13 as well as trimethylamine were only weak inhibitors when incubated alone. In the presence of inorganic pyrophosphate, itself a known competitive inhibitor of trichodiene synthase, all five amines showed strong cooperative competitive inhibition with an enhancement factor estimated to be 10-40. The apparent induced inhibition constant alpha-K(j) decreased in going from trimethylamine to the monoterpene analogs 13 and was strongest for the sesquiterpene analogs 16, indicating that both electrostatic and hydrophobic interactions are important in the binding of each intermediate analog. The cyclase showed little discrimination, however, between the individual enantiomers of each inhibitor.

  DOI：

  10.1021/jo00038a040

文献信息

• Identification and synthesis of (Z)-(1′S,3′R,4′S)(–)-2-(3′,4′-epoxy-4′-methylcyclohexyl)-6-methylhepta-2,5-diene, the sex pheromone of the southern green stinkbug, Nezara viridula(L.)
  作者：Raymond Baker、Miguel Borges、Nigel G. Cooke、Richard H. Herbert

  DOI：10.1039/c39870000414

  日期：——

  The sex pheromone of the male green stinkbug, Nezara viridula(L.) has been shown to be a novel epoxybisabolene (Z)-(1′S,3′R,4′S)(–)-2-(3′,4′-epoxy-4′-methylcyclohexyl)-6-methylhepta-2,5-diene, whose structure has been confirmed by spectroscopic studies and synthesis of the eight possible stereoisomers.

  阳绿椿象的性信息素，稻绿蝽（L.）已被证明是一种新颖epoxybisabolene（Ž） - （1'小号，3' - [R，4'小号）（ - ） - 2-（3'， 4'-环氧-4'-甲基环己基）-6-甲基庚-2,5-二烯的结构已通过光谱研究和八种可能的立体异构体的合成得到证实。
• Viable route and DFT study for the synthesis of optically active limonaketone: A barely available natural feedstock in Cedrus atlantica
  作者：Ayoub Abdelkader Mekkaoui、Hicham Ben El Ayouchia、Hafid Anane、Rachid Chahboun、Larbi El Firdoussi、Soufiane El Houssame

  DOI：10.1016/j.molstruc.2021.130221

  日期：2021.7

  Herein, we report a novel, easy and efficient synthesis pathway of optically active limonaketone, a high added value monoterpene, starting from limonene, natural and low-cost feedstock. The strategy was developed in an excellent three-step total synthesis of limonaketone, potentially important intermediate in limonene ozonolysis and barely available in Cedrus Atlantica essential oil (0.1% yield). The

  在本文中，我们报道了从柠檬烯，天然和低成本原料开始的光学活性柠檬烯酮（一种高附加值的单萜）的新颖，简便，有效的合成途径。该策略是通过出色的三步全合成柠檬烯酮开发的，柠檬烯酮是柠檬烯臭氧分解中潜在的重要中间体，在Cedrus Atlantica中几乎没有精油（0.1％收率）。第一步是柠檬烯的环氧化，产率为91％。所制备的柠檬烯氧化物的臭氧分解导致柠檬烯酮的特征酮功能的形成，产率为92％。最后的步骤是在Zn存在下通过脱氧进行的，并以定量收率得到柠檬烯酮。由柠檬烯有效地合成了光学纯的柠檬烯酮，总产率为84％。通过在M06-2X / 6-311G（d，p）（Zn的LANL2DZ）水平使用密度泛函理论（DFT）计算进行了分子电子密度理论（MEDT）分析，以了解在Zn-中观察到的化学选择性。脱氧反应及其相应的机理途径。
• Stereocontrolled Synthesis of the Sex Pheromones of the Green Stink Bug
  作者：B. E. Marron、K. C. Nicolaou

  DOI：10.1055/s-1989-27309

  日期：——

  The four diastereoisomeric 3′,4′-epoxides of (Z)-α-bisabolene, (+)-1, (+)-2, (-)-1 and (+)-2, have been synthesized by stereocontrolled sequences. Comparisons with natural materials collected from the stink bug Nezara viridula revealed that the pheromone blend of this species contains (+)-1 or (-)-2 as major epoxide and (+)-2 or (-)-1 as minor epoxide in varying ratios depending on the geographical site of collection.

  通过立体控制序列合成了(Z)-δ-bisabolene的四种非对映异构体3′,4′-环氧化物，即(+)-1、(+)-2、(-)-1和(+)-2。通过与从蝽类 Nezara viridula 采集的天然材料进行比较，发现该物种的信息素混合物中主要环氧化物为 (+)-1 或 (-)-2，次要环氧化物为 (+)-2 或 (-)-1，其比例因采集地点而异。
• MARRON, B. E.;NICOLAOU, K. C., SYNTHESIS (BRD),(1989) N, C. 537-539
  作者：MARRON, B. E.、NICOLAOU, K. C.

  DOI：——

  日期：——
• Trichodiene synthase. Synergistic inhibition by inorganic pyrophosphate and aza analogs of the bisabolyl cation.
  作者：David E. Cane、Guohan Yang、Robert M. Coates、Hyung Jung Pyun、Thomas M. Hohn

  DOI：10.1021/jo00038a040

  日期：1992.6

  A series of aza analogs of the bisabolyl and alpha-terpinyl cations were tested as inhibitors of the sesquiterpene cyclase, trichodiene synthase. Both (R)- and (S)-16 and (R)- and (S)-13 as well as trimethylamine were only weak inhibitors when incubated alone. In the presence of inorganic pyrophosphate, itself a known competitive inhibitor of trichodiene synthase, all five amines showed strong cooperative competitive inhibition with an enhancement factor estimated to be 10-40. The apparent induced inhibition constant alpha-K(j) decreased in going from trimethylamine to the monoterpene analogs 13 and was strongest for the sesquiterpene analogs 16, indicating that both electrostatic and hydrophobic interactions are important in the binding of each intermediate analog. The cyclase showed little discrimination, however, between the individual enantiomers of each inhibitor.