6,7-pentadecadien-1-yne | 203449-12-1

• 分子结构分类: 有机化合物 - 乙炔化物
• 英文名称: 6,7-pentadecadien-1-yne
• CAS: 203449-12-1
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: AYFSAESXXVIWQR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  15
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  6,7-pentadecadien-1-yne 在 copper(l) iodide 、 四(三苯基膦)钯 、 bis(1,5-cyclooctadiene)diiridium(I) dichloride 作用下， 以 二乙胺 、 甲苯 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 16.0h， 生成 1-heptyl-3-phenyl-1,4,5,6-tetrahydro-inden-2-one
  参考文献：
  名称：

  An Allenic Pauson−Khand-Type Reaction:  A Reversal in π-Bond Selectivity and the Formation of Seven-Membered Rings

  摘要：

  [GRAPHICS]Treatment of alkynyl allenes with [Rh(CO)(2)Cl](2) results in a formal [2 + 2 + 1] cycloaddition reaction. This reaction occurs with complete regioselectivity for a variety of substrates affording only 4-alkylidene cyclopentenones in good yields. Moreover, seven-membered rings have been prepared in high yields.

  DOI：

  10.1021/ol025955w
• 作为产物：
  描述：

  (5-氯-1-戊炔基)三甲基硅烷 在 四丁基氟化铵 、 氢化钾 、 copper(I) bromide 、 lithium bromide 、 magnesium chloride 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 6,7-pentadecadien-1-yne
  参考文献：
  名称：

  An Intramolecular Allenic [2 + 2 + 1] Cycloaddition

  摘要：

  A new stereo- and regioselective method for the preparation of alpha-methylene and 4-alkylidene cyclopentenones is described. These substructures were achieved by an intramolecular [2 + 2 + 1] cycloaddition of an allene, alkyne, and carbon monoxide moieties to afford the target compounds stereoselectively and in good yields. In some cases, the target compounds were obtained as mixtures, but it is demonstrated that the formation of either the alpha-methylene or 4-alkylidene cyclopentenone can be controlled by the allene structure or reaction conditions. Monosubstituted allenes afford alpha-methylene cyclopentenones as the only cycloadduct. Disubstitution on the allene alters the course of the allenic [2 + 2 + 1] reaction. 3,3-Disubstituted allenes undergo cycloaddition with the least substituted pi-bond of the allene. This affords the bicyclo[4.3.0]nonane ring system. Cycloaddition of 1,3-disubstituted allenes afford mixtures of several possible cycloadducts. However, it has been shown that good control over the product ratio can be obtained by altering the cycloaddition conditions and that the regiochemistry can be directed depending upon the metal used.

  DOI：

  10.1021/jo980548c

文献信息

• Chiral Nonracemic α-Alkylidene and α-Silylidene Cyclopentenones from Chiral Allenes Using an Intramolecular Allenic Pauson−Khand-Type Cycloaddition
  作者：Kay M. Brummond、Angela D. Kerekes、Honghe Wan

  DOI：10.1021/jo016305t

  日期：2002.7.1

  effected a transfer of chirality from a chiral nonracemic allene to an alpha-alkylidene and an alpha-silylidene cyclopentenone. The molybdenum-mediated examples possessing a silyl group on the terminus of the allene show good facial selectivities, but isomerization of the (E)-silylidene cyclopentenone to the (Z)-silylidene cyclopentenone occurs upon purification of these products. Alternatively, an alkyl group

  我们已经成功地实现了手性从手性非外消旋烯到α-亚烷基和α-亚甲硅烷基环戊烯酮的转移。在丙二烯末端具有甲硅烷基的钼介导的实例显示出良好的面部选择性，但是在纯化这些产物时，（E）-亚甲基环戊烯酮异构化为（Z）-亚甲基环戊烯酮。或者，在丙二烯末端上的烷基以适度的选择性进行环加成反应，但当暴露于酸性条件下时，其产物会经历（Z）-亚烷基环戊烯酮异构化为（E）-亚烷基环戊烯酮。因此，由于该异构化，观察到两种产物之一对映体过量的侵蚀。烯丙基Pauson-Khand型环加成反应也已通过首先分离（eta（6）-亚芳基）三羰基钼钼络合物而实现，这首次证明这很可能是钼介导的反应中的活性络合物。试图通过增加芳烃部分的大小来增加面部选择​​性，导致选择性的增加，但以收率为代价。基于这些结果，我们得出结论，为了获得合成上有用的立体控制水平，必须改变制备非外消旋α-亚烷基环戊烯酮的方法。试图通过增加芳烃部分的大小来增加
• The allenic Pauson-Khand cycloaddition. Dependence in π-bond selectivity on substrate structure
  作者：Kay M. Brummond、Honghe Wan

  DOI：10.1016/s0040-4039(97)10679-7

  日期：1998.2

  Alkynyl allenes undergo intramolecular Pauson-Khand (P-K) cycloadditions to provide functionalized α-methylene and 4-alkylidene cyclopentenones in good yields. These studies have demonstrated a dependence of the π-bond selectivity of this cycloaddition on the substitution pattern of the allene.

  炔基丙二烯进行分子内的Pauson-Khand（PK）环加成反应，以高收率提供官能化的α-亚甲基和4-亚烷基环戊烯酮。这些研究已经证明，该环加成的π键选择性依赖于丙二烯的取代模式。
• An Allenic Pauson−Khand-Type Reaction:  A Reversal in π-Bond Selectivity and the Formation of Seven-Membered Rings
  作者：Kay M. Brummond、Hongfeng Chen、Kimberly D. Fisher、Angela D. Kerekes、Brenden Rickards、Peter C. Sill、Steven J. Geib

  DOI：10.1021/ol025955w

  日期：2002.5.1

  [GRAPHICS]Treatment of alkynyl allenes with [Rh(CO)(2)Cl](2) results in a formal [2 + 2 + 1] cycloaddition reaction. This reaction occurs with complete regioselectivity for a variety of substrates affording only 4-alkylidene cyclopentenones in good yields. Moreover, seven-membered rings have been prepared in high yields.
• An Intramolecular Allenic [2 + 2 + 1] Cycloaddition
  作者：Kay M. Brummond、Honghe Wan、Joseph L. Kent

  DOI：10.1021/jo980548c

  日期：1998.9.1

  A new stereo- and regioselective method for the preparation of alpha-methylene and 4-alkylidene cyclopentenones is described. These substructures were achieved by an intramolecular [2 + 2 + 1] cycloaddition of an allene, alkyne, and carbon monoxide moieties to afford the target compounds stereoselectively and in good yields. In some cases, the target compounds were obtained as mixtures, but it is demonstrated that the formation of either the alpha-methylene or 4-alkylidene cyclopentenone can be controlled by the allene structure or reaction conditions. Monosubstituted allenes afford alpha-methylene cyclopentenones as the only cycloadduct. Disubstitution on the allene alters the course of the allenic [2 + 2 + 1] reaction. 3,3-Disubstituted allenes undergo cycloaddition with the least substituted pi-bond of the allene. This affords the bicyclo[4.3.0]nonane ring system. Cycloaddition of 1,3-disubstituted allenes afford mixtures of several possible cycloadducts. However, it has been shown that good control over the product ratio can be obtained by altering the cycloaddition conditions and that the regiochemistry can be directed depending upon the metal used.