3,3-dimethyl-4,5,6-trihydro-2H-pentalen-1-one | 72233-31-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,3-dimethyl-4,5,6-trihydro-2H-pentalen-1-one
• 英文别名: 3,3-dimethyl-3,4,5,6-tetrahydro-1(2H)-pentalenone；3,3-dimethyl-2,4,5,6-tetrahydropentalen-1-one
• CAS: 72233-31-9
• 化学式: C₁₀H₁₄O
• 分子量: 150.221
• InChiKey: PECJLLWRMRWDHH-UHFFFAOYSA-N

物化性质

• 沸点：
  241.4±7.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3,3-dimethyl-4,5,6-trihydro-2H-pentalen-1-one 在 disodium hydrogenphosphate 、 copper(l) iodide 、 三氟化硼乙醚 、 potassium tert-butylate 、 四丁基氟化铵 、 碘 、 potassium carbonate 、 一水合肼 、 magnesium 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 异丙醚 、 水 、 萘烷 、 二乙二醇 、 苯 为溶剂， 反应 41.75h， 生成 modhephene
  参考文献：
  名称：

  [3.3.3]丙炔倍半萜的高度立体控制的合成。（±）-莫非芬和（±）-亚庚基

  摘要：

  据报道立体特异性合成了（±）-二苯乙（2）和（±）-表二烯（3）。共轭加成1-三甲基甲硅烷基-1-丁炔-4-基铜酸酯（BF 3-醚酸酯催化）到双环酮6，氟化物离子促进末端乙炔的解封，和烯反应，得到三环烯酮11。连续的维蒂希甲基化，区域控制的环氧化和路易斯酸催化的异构化提供了酮14，其双键重定位和Wolff-Kishner还原仅导致2。在到3的更短路径中，将6的3-丁烯基铜酸酯加到了7上。。发现该中间体的热解，亚甲基化和双键异构化成功地递送了纯3。

  DOI：

  10.1016/0040-4020(81)80009-9
• 作为产物：
  描述：

  1-甲基环戊烯 在 三氯化铝 作用下， 以 二氯甲烷 为溶剂， 反应 7.0h， 生成 3,3-dimethyl-4,5,6-trihydro-2H-pentalen-1-one
  参考文献：
  名称：

  Acylation of alkenes generated in situ by hydride transfer from isoalkanes. Synthesis of pentalenones, hydrindenones, and cyclopentenones

  摘要：

  Acylation, in the presence of AlCl3 and hydride acceptor, of methylcyclopentane, methylcyclohexane, and 2-methylbutane by ethylenic acyl chlorides, in CH2Cl2 solution, respectively, leads to tetrahydropentalenones, tetrahydroindenones, and cyclopentenones in good yields. Hydride acceptor may be either acetyl chloride or the alkenoyl chloride itself. Better results are performed in the presence of nitromethane and CuSO4. Overall yields are better than those obtained by the two-step process involving acylation of alkenes by alkenoyl chlorides and subsequent Nazarov cyclization of the resulting divinylketones. Methyl 1,4-migration is observed during the acylation of 2-methylbutane by sorboyl chloride. The mechanism of these conversions is discussed on the basis of results observed with cyclohexane-d12 and methylbutane-d6 as well as stereochemical studies of the cyclization process.

  DOI：

  10.1021/ja00021a036

文献信息

• Highly stereocontrolled synthesis of [3.3.3] propellane sesquiterpenes. ( ± )-Modhephene and (±)-epimodhephene
  作者：Heinrich Schostarez、Leo A. Paquette

  DOI：10.1016/0040-4020(81)80009-9

  日期：1981.1

  Stereospecific total synthesis of (±)-modhephene (2) and (±)-epimodhephene (3) are reported. Conjugate addition of 1-trimethylsilyl-1-butyn-4-yl cuprate (BF3-etherate catalysis) to bicyclic ketone 6, fluoride ion-promoted deblocking of the terminal acetylene, and ene reaction, gave tricyclic enone 11. Sequential Wittig methylenation, regiocontrolled epoxidation, and Lewis acid catalyzed isomerization

  据报道立体特异性合成了（±）-二苯乙（2）和（±）-表二烯（3）。共轭加成1-三甲基甲硅烷基-1-丁炔-4-基铜酸酯（BF 3-醚酸酯催化）到双环酮6，氟化物离子促进末端乙炔的解封，和烯反应，得到三环烯酮11。连续的维蒂希甲基化，区域控制的环氧化和路易斯酸催化的异构化提供了酮14，其双键重定位和Wolff-Kishner还原仅导致2。在到3的更短路径中，将6的3-丁烯基铜酸酯加到了7上。。发现该中间体的热解，亚甲基化和双键异构化成功地递送了纯3。
• Regioselective Silver-Mediated Kondakov-Darzens Olefin Acylation
  作者：Nicholas T. Barczak、Elizabeth R. Jarvo

  DOI：10.1002/chem.201102476

  日期：2011.11.11

  Enone construction: A silver‐mediated olefin acylation reaction is described, in which five‐, six‐, and ‐seven‐membered rings, tetrasubstituted olefins, bridged bicycles, spirocycles, and benzoxepinones are prepared. Highly selective intermolecular reactions are coupled to a Nazarov cyclization for the effective preparation of cyclopentenones, including the core of modhephene (see scheme).

  烯酮的结构：描述了一种银介导的烯烃酰化反应，其中制备了五元，六元和七元环，四取代的烯烃，桥连的自行车，螺环和苯并庚二酮。高度选择性的分子间反应与Nazarov环化反应相结合，可有效制备环戊烯酮，包括莫非芬的核心（参见方案）。
• A Short and Efficient Synthesis of (±)-Modhephene by a Stereoelectronically-Controlled Ene-Reaction
  作者：Wolfgang Oppolzer、Kurt Bättig

  DOI：10.1002/hlca.19810640756

  日期：1981.11.4

  (±)-Modhephene (6) has been synthesized from the easily available trimethylpentalenone 1 in 6 steps in 26% overall yield (Scheme 2). The remarkably smooth 1,4-addition/enolate trapping 1 2 and subsequent selenoxide elimination after oxidation furnished the key intermediate 3 which underwent an expedient and highly stereoselctive intramolecular ene-reaction to give the propellane 4, readily convertible

  （±）-Modhephene（6）是由易于获得的三甲基戊烯酮1分6个步骤合成的，总产率为26％（方案2）。明显光滑的1,4加成/烯醇盐捕集1 2和随后氧化后的亚硒酸酯消除提供了关键中间体3，该中间体进行了方便且高度立体选择性的分子内烯反应，生成了易于转化为（±）-6的丙炔4。
• Intramolecular radical cyclization of silylacetylenic or olefinic α-iodo ketones: Application to the total synthesis of (±)-modhephene
  作者：Sha Chin-Kang、Jean Tsong-Shin、Wang Deh-Chi

  DOI：10.1016/s0040-4039(00)97460-4

  日期：——

  Silylacetylenic or olefinic α-iodo ketones were treated with tributyltin hydride and AIBN to give bicyclic ketones by an intramolecular α-carbonyl radical cyclization reaction. As an application of this radical cyclization reaction, the total synthesis of (±)-modhephene has been accomplished efficiently.

  用氢化三丁基锡和AIBN处理甲硅烷基或烯属α-碘酮，通过分子内α-羰基自由基环化反应得到双环酮。作为该自由基环化反应的一种应用，已经有效地完成了（±）-二苯乙烯的全合成。
• Vinylsilane mediated regiospecific cyclopentenone annulation of ketones
  作者：William E. Fristad、David S. Dime、Bailey Thomas R、Paquette Leo A

  DOI：10.1016/s0040-4039(01)86247-x

  日期：1979.1

  The development of a new cyclopentenone annulation sequence of general scope which involves Friedel-Crafts acylation of a vinylsilane with an α,β-unsaturated acid chloride followed by Nazarov cyclization is reported.

  据报道，开发了一种新的通用范围的环戊烯酮环化顺序，该顺序涉及乙烯基硅烷与α，β-不饱和酰氯的弗瑞德-克来福特（Friedel-Crafts）酰化，然后进行纳扎罗夫环化。