(-)-α-necrodol | 104104-38-3

• 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: (-)-α-necrodol
• 英文别名: [(1R,4R)-3,4,5,5-tetramethylcyclopent-2-en-1-yl]methanol
• CAS: 104104-38-3
• 化学式: C₁₀H₁₈O
• 分子量: 154.252
• InChiKey: KMSIDXMGNKQFNQ-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 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：

  (-)-α-necrodol 、 异丁酰氯 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 (1R,4R)-(3,4,5,5-tetramethyl-2-cyclopentenyl)methyl isobutyrate
  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：

  ethyl (1R,3S,4S)-4-hydroxy-2,2,3-trimethylcyclopentane carboxylate 在 lithium aluminium tetrahydride 、 草酰氯 、 四氯化钛 、 lithium 、 二甲基亚砜 、 乙二胺 、 三乙胺 、 锌 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 3.15h， 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

文献信息

• 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）。
• KINETIC RESOLUTION REACTION OF A (1RS,2SR)-(2-HYDROXY-3,5,5-TRIMETHYL-3-CYCLOPENTENYL)METHYL CARBOXYLATE COMPOUND, A PROCESS FOR PREPARING OPTICALLY ACTIVE TRANS-alpha-NECRODYL ISOBUTYRATE, AND A PROCESS FOR PREPARING OPTICALLY ACTIVE gamma-NECRODYL ISOBUTYRATE
  申请人：Shin-Etsu Chemical Co., Ltd.

  公开号：US20220234983A1

  公开（公告）日：2022-07-28

  The present invention relates to a process for preparing a (1S,2R)-(2-hydroxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound of the following general formula (S,R)-(2), wherein R 1 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a bold wedged bond represents the absolute configuration, and a (1R,2S)-(2-acetoxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound of the following general formula (R,S)-(3), wherein R 1 is as defined above, a hashed wedged bond represents the absolute configuration, and Ac represents an acetyl group, the process comprising: subjecting a (1RS,2SR)-(2-hydroxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound of the following general formula (RS,SR)-(2), wherein R 1 is as defined above, and a hashed unwedged bond represents a relative configuration, to a kinetic resolution reaction with a lipase in the presence of vinyl acetate to obtain the (1S,2R)-(2-hydroxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound ((S,R)-(2)) and the (1R,2S)-(2-acetoxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound ((R,S)-(3)).

  本发明涉及一种制备以下通式（S，R）-（2）的（1S，2R）-（2-羟基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物的方法，其中R1表示具有1至6个碳原子的一价烃基，粗体楔头线代表绝对构型，以及以下通式（R，S）-（3）的（1R，2S）-（2-乙酰氧基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物，其中R1如上定义，哈希楔头线代表绝对构型，Ac代表乙酰基，该方法包括：将以下通式（RS，SR）-（2）的（1RS，2SR）-（2-羟基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物，其中R1如上定义，哈希未楔头线代表相对构型，与脂肪酶在乙酸乙烯酯存在下进行动力学分辨反应，以获取（1S，2R）-（2-羟基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物（（S，R）-（2））和（1R，2S）-（2-乙酰氧基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物（（R，S）-（3））。
• Defense mechanisms of arthropods. 84. Synthesis of (-)-.alpha.-necrodol and (-)-.beta.-necrodol: novel cyclopentanoid terpenes from a carrion beetle
  作者：Robert T. Jacobs、Geoffrey I. Feutrill、Jerrold Meinwald

  DOI：10.1021/jo00300a021

  日期：1990.6
• Defense mechanisms of arthropods. 83. .alpha.- and .beta.-Necrodol, novel terpenes from a carrion beetle (Necrodes surinamensis, Silphidae, Coleoptera)
  作者：Braden Roach、Thomas Eisner、Jerrold Meinwald

  DOI：10.1021/jo00300a020

  日期：1990.6
• Synthesis of α-Necrodol:  Unexpected Formation of a Cyclopropene
  作者：Douglass F. Taber、Han Yu

  DOI：10.1021/jo961780q

  日期：1997.3.1

  Significant 1,3-induction in intramolecular alkylidene C-H insertion is reported. Thus, exposure of ketone I to the lithium salt of (trimethylsilyl)diazomethane provides a 2.4:1.0 ratio of IIa and IIIa, which are deprotected to alpha-necrodol IIb and the epimeric IIIb. The 1,3-insertion product cyclopropene IV was also formed.