5,5-dimethyl-3-phenyl-2-cyclopenten-1-one | 5395-41-5

• 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: 5,5-dimethyl-3-phenyl-2-cyclopenten-1-one
• 英文别名: 5,5-dimethyl-3-phenylcyclopent-2-en-1-one；5,5-dimethyl-3-phenyl-2-cyclopentenone；5,5-dimethyl-3-phenylcyclopent-2-enone
• CAS: 5395-41-5
• 化学式: C₁₃H₁₄O
• 分子量: 186.254
• InChiKey: DHDAHIRKCHKSKA-UHFFFAOYSA-N

物化性质

• 沸点：
  250.4±25.0 °C(Predicted)
• 密度：
  1.039±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1-异亚丙基-3-苯基-2-环丁烯 在 水 、 溴 、 silica gel 作用下， 以 二氯甲烷 为溶剂， 生成 5,5-dimethyl-3-phenyl-2-cyclopenten-1-one
  参考文献：
  名称：

  亚烷基环丁烯的亲电子加成中的环外区域选择性惊人

  摘要：

  向亚烷基环丁烯中添加过酸，溴，TCNE和单线态氧显示出对环外双键的强烈区域选择性（在某些情况下为区域特异性）。取决于试剂，内环双键将仅在添加第二当量的试剂时发生反应。在前三种试剂的情况下，通过调用更稳定的碳正离子中间体或过渡态的形成来合理化这种环外区域选择性。关于1 O 2，其中极性机制很少，我们将此环外区域选择性归因于不适当的排列，因此缺乏环内烯丙基氢的反应性。

  DOI：

  10.1016/s0040-4020(02)00267-3

文献信息

• Carbopalladation of Nitriles:  Synthesis of Benzocyclic Ketones and Cyclopentenones via Pd-Catalyzed Cyclization of ω-(2-Iodoaryl)alkanenitriles and Related Compounds
  作者：Alexandre A. Pletnev、Richard C. Larock

  DOI：10.1021/jo0262006

  日期：2002.12.1

  An efficient procedure for the synthesis of 2,2-disubstituted benzocyclic ketones by intramolecular carbopalladation of nitriles has been developed. The cyclization of substituted 3-(2-iodoaryl)propanenitriles affords indanones in high yields. The reaction is compatible with a wide variety of functional groups. This methodology has been extended to the synthesis of tetralones and cyclopentenones.

  已经开发出一种通过腈的分子内碳弹头化合成2，2-二取代的苯并环酮的有效方法。取代的3-（2-碘芳基）丙烷腈的环化以高收率提供茚满酮。该反应与多种官能团相容。该方法已经扩展到四氢萘酮和环戊烯酮的合成。
• Cyclocarbonylation of acyclic 1,3-dienes via their tricarbonyl iron complexes : Cyclopenten-2-ones and dicarbonyl cyclopentadienyl iron halides
  作者：Michel Franck-Neumann、Enrique Luis Michelotti、Roland Simler、Jean-Michel Vernier

  DOI：10.1016/s0040-4039(00)60188-0

  日期：1992.11

  of acyclic 1,3-dienes can be converted to conjugated cyclopentenones by decomplexation with aluminium halides. Most complexes of a simple dienes need drastic conditions for the cyclocarbonylation to occur (100 Atm CO, 1000° C), with the exception of 1,1,3-trialkylbutadiene complexes which are nearly quantitatively converted into cyclopentenones at room temperature, even in the absence of a CO atmosphere

  无环1，3-二烯的三羰基铁配合物可通过与卤化铝解络而转化为共轭的环戊烯酮。大多数简单的二烯络合物都需要苛刻的条件才能发生环羰基化反应（100 Atm CO，1000°C），除了1,1,3-三烷基丁二烯络合物几乎可以在室温下定量转化为环戊烯，即使在室温下也是如此。没有CO气氛。在相同的温和条件下，其他配合物通过环羰基化反应以中等收率生成环戊二烯基二羰基卤化铁，然后通过卤化铝促进脱氧。
• Regio- and Stereoselective Synthesis of Cyclopentenones: Intermolecular Pseudo-Pauson-Khand Cyclization
  作者：José Barluenga、Ana Álvarez-Fernández、Ángel L. Suárez-Sobrino、Miguel Tomás

  DOI：10.1002/anie.201105362

  日期：2012.1.2

  two‐step access to polysubstituted cyclopentenones from terminal alkynes, [M(CO)6], and bromoalkenes is described. This protocol is an alternative to the intermolecular Pauson–Khand reaction, and can be used with a variety of bromoalkenes. Moreover, the final quenching allows the installation of reactive electrophiles (E). The enantiopure product cyclopentenones can be synthesized with an all‐carbon‐substituted

  分两步进行：描述了非常简单的两步访问末端炔烃[M（CO）6 ]和溴代烯烃的多取代环戊烯酮的方法。该方案是分子间Pauson-Khand反应的替代方案，可用于多种溴代烯烃。而且，最后的淬灭允许安装反应性亲电试剂（E）。对映体纯产物环戊烯酮可以与全碳取代的季立体中心合成。
• Rearrangement of 1-(1-Alkynyl)cyclopropanols to 2-Cyclopentenones via Their Hexacarbonyldicobalt Complexes. A New Use of Alkyne−Co₂(CO)₆ Complexes in Organic Synthesis
  作者：Nobuharu Iwasawa、Takeshi Matsuo、Mari Iwamoto、Taketo Ikeno

  DOI：10.1021/ja9734004

  日期：1998.4.1

  protective group of the substrates. This rearrangement was successfully applied to cyclopentenone annulation reactions onto cycloalkenes. An efficient synthesis of alkynyl-substituted bicyclo[n.1.0]alkanol derivatives from the corresponding cycloalkenes according to Danheiser's protocol was developed, and bicyclic cyclopentenones were obtained in moderate to good yield by applying to these the cobalt-mediated

  1-(1-炔基) 环丙醇向 2-环戊烯-1-酮的新重排是在其炔基部分与八羰基二钴 (Co2(CO8)) 络合后进行的。1-(1-炔基) 环丙醇在其炔烃末端具有广泛的取代基，以良好的产率重排为相应的 3-取代的 2-环戊烯-1-酮。In case of the reactions of 1-alkynylcyclopropanols with an alkyl substituent on the cyclopropane ring, either 4-substituted or 5-substituted 2-cyclopenten-1-ones could be selectively obtained by appropriate choice of stereochemistry and protective group of the substrates. 这种重排成功地应用于环戊烯酮环化成环烯烃的反应。根据
• A Conformationally Controlled Regioselective Rearrangement of 2-Substituted 1-Alkynylcyclopropanols to 2-Cyclopenten-1-ones via Hexacarbonyldicobalt Complex
  作者：Nobuharu Iwasawa、Mari Iwamoto

  DOI：10.1246/cl.1993.1257

  日期：1993.7

  The rearrangement of hexacarbonyldicobalt-complexed 2-substituted 1-alkynylcyclopropanol derivatives is conformationally controlled to give 4- or 5-substituted 2-cyclopentenones regioselectively. In the cases of the reactions of 2-monosubstituted 1-alkynylcyclopropanol derivatives, either regioisomer can be selectively obtained by the appropriate choice of the substrates.

  六羰基二钴络合的 2-取代的 1-炔基环丙醇衍生物的重排受到构象控制，以区域选择性地得到 4-或 5-取代的 2-环戊烯酮。In the cases of the reactions of 2-monosubstituted 1-alkynylcyclopropanol derivatives, either regioisomer can be selectively obtained by the appropriate choice of the substrates.