(-)-(1R,3R)-ethyl 2,3,3-trimethyl-4-methylidenecyclopentanemethanol | 104086-70-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (-)-(1R,3R)-ethyl 2,3,3-trimethyl-4-methylidenecyclopentanemethanol
• 英文别名: (2,2,3-trimethyl-4-methylenecyclopentyl)methanol；(-)-(R,R)-β-necrodol；(-)-β-necrodol；β-necrodol；2,2,3-trimethyl-4-methylenecyclopentanemethanol；[(1R,3R)-2,2,3-trimethyl-4-methylidenecyclopentyl]methanol
• CAS: 104086-70-6
• 化学式: C₁₀H₁₈O
• 分子量: 154.252
• InChiKey: QPEVOWJNFFZVOF-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  (-)-(1R,3R)-ethyl 2,3,3-trimethyl-4-methylidenecyclopentanemethanol 在 lithium 、 乙二胺 作用下， 反应 0.15h， 生成 (-)-α-necrodol
  参考文献：
  名称：

  Synthesis and Bioassay of Racemic and Chiral trans-α-Necrodyl Isobutyrate, the Sex Pheromone of the Grape Mealybug Pseudococcus maritimus

  摘要：

  A concise synthesis of the racemic form of the female-produced pheromone of the grape mealybug was developed. The synthesis was readily adapted to production of both enantiomers of the pheromone via lipase-catalyzed kinetic resolution of an intermediate in the synthesis. Replicated field trials revealed that, contrary to a preliminary report, the (R,R)- rather than the (S,S)-enantiomer is the attractive stereoisomer. Lithium aluminum hydride reduction of the insect-produced compound to a-necrodol followed by analysis on a chiral stationary phase GC column showed that the insect-produced material was actually an 85:15 mixture of the (R,R)- and (S,S)-enantiomers. The racemic form of the pheromone was highly attractive to male mealybugs, and in one of two field bioassays, the racemic material was significantly more attractive than the pure (R,R)-enantiomer, suggesting that the (S,S)-enantiomer might act synergistically.

  DOI：

  10.1021/jf904452v
• 作为产物：
  描述：

  methyl phenylcamphorate 在 sodium periodate 、 lithium aluminium tetrahydride 、 四氧化钌 、 三丁基膦 、 硼烷 、 sodium methylate 、 二异丙胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 乙醚 、 水 、 乙腈 为溶剂， 反应 205.0h， 生成 (-)-(1R,3R)-ethyl 2,3,3-trimethyl-4-methylidenecyclopentanemethanol
  参考文献：
  名称：

  Defense mechanisms of arthropods. 84. Synthesis of (-)-.alpha.-necrodol and (-)-.beta.-necrodol: novel cyclopentanoid terpenes from a carrion beetle

  摘要：

  DOI：

  10.1021/jo00300a021

文献信息

• Conversion of Campholene- to Necrodane-Type Monoterpenes. A short stereoselective synthesis of (?)-(R,R)-?-necrodol and its three stereoisomers
  作者：Karl H. Schulte-Elte、Herv� Pamingle

  DOI：10.1002/hlca.19890720534

  日期：1989.8.9

  Application of a stereoselective Prins/retro-Prins rearrangement sequence from (−)-(R)-campholenyl acetate((−)-4) opens a new access to the naturally occurring (−)-(R, R)-β-necrodol ((−)-1) and its three stereoisomers with high optical purity.

  立体选择性Prins / retro的应用-从（-）-（R）-樟脑烯基乙酸酯（（-）- 4）的Prins重排序列为天然存在的（-）-（R，R）-β-肾上腺素开辟了新途径（（-）- 1）及其三种具有高光学纯度的立体异构体。
• A Synthesis of β-necrodol via a palladium catalyzed reductive enyne cyclization
  作者：Barry M. Trost、Rebecca Braslau

  DOI：10.1016/s0040-4039(00)80263-4

  日期：1988.1

  The Pd catalyzed reductive enyne cyclization provides an approach to control 1,3- diastereoselectivity and thereby provides a five step synthesis of β-necrodol, a key substituent of the defensive secretion of the red-lined carrion beetle.

  Pd催化的还原性烯炔环化提供了一种控制1,3-非对映选择性的方法，从而提供了五步合成β-necrodol（β-necrodol）的方法，β-necrodol是红线腐肉甲虫防御性分泌物的关键取代基。
• Enantioselective Synthesis of ?-Necrodol and of 1-Epi-?-necrodolvia Asymmetric 1,4-Addition and Magnesium-Ene Cyclization. Preliminary Communication
  作者：Wolfgang Oppolzer、Philippe Schneider

  DOI：10.1002/hlca.19860690805

  日期：1986.12.10

  Enantiomerically pure β-necrodol (1) and its 1-epimer 16 have been synthesized starting from aldehyde 5. The two key steps are an asymmetric conjugate addtion/Mannich reaction tandem (1012) and a type-II-magnesiumene cyclization/oxidation sequence (141 + 16).

  对映体纯的β-necrodol（1）及其1 -epimer 16已从醛5开始合成。这两个关键步骤是不对称共轭加成/曼尼希反应串联（10 12）和II型镁烯环化/氧化序列（14 1 + 16）。
• Stereoselective Conversion of Campholene- to Necrodane-Type Monoterpenes. Novel Access to (?)-(R,R)- and (R,S)-?-Necrodol and the Enantiomeric ?-Necrodols
  作者：Herv� Pamingle、Roger L. Snowden、Karl H. Schulte-Elte

  DOI：10.1002/hlca.19910740310

  日期：1991.5.2

  Naturally occurring (−)-(R,R)-α-necrodol ((−)-1) and its C(4)-epimer (−)-2 are obtained in 84 and 44% yields, respectively, by lithium ethylenediamide (LEDA) treatment of the corresponding β-necrodols (−)-3 and (−)-4 (Scheme 1, Table), both readily available from (−)-campholenyl acetate ((−)-i) by an efficient stereoselective synthesis. The thermodynamically preferred (−)-(R)-γ-necrodol ((−)-5) becomes the

  天然生成的（-）-（R，R）-α-肾上腺素（（-）- 1）及其C（4）-顶基（-）- 2通过乙二酰胺锂（分别为84％和44％的收率（ LEDA）处理相应的β-necrodols（-）- 3和（-）- 4（方案1，表），它们都可以通过有效的立体选择性合成容易地从（-）-樟脑烯基乙酸酯（（-）- i）获得。经过长时间的LEDA处理或将α-和β-necrodols暴露于BF 3 ·后，热力学上优选的（-）-（R）-γ-necrodol（（-）- 5）成为主要产物（≥80％收率）。等2O.在另一种方法中，从（+）-樟脑（（+）- ii）经由Pd催化的脱羰基反应生成（-）-（S）-1,4,5,5-来制备（+）- 5四甲基环戊-1-烯（（-）- 6）和随后施加酸催化的CH 2 O加/重排序列（方案2）。
• Enzyme-Assisted Enantioselective Synthesis of Natural (−)-β-Necrodol and Its Enantiomer
  作者：Jean-Marie Galano、Gérard Audran、Lionel Mikolajèzyk、Honoré Monti

  DOI：10.1021/jo0013812

  日期：2001.1.1