(Z)-2-phenyl-5-(trimethylsilyl)pent-2-en-4-yn-1-ol | 250358-91-9

• 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: (Z)-2-phenyl-5-(trimethylsilyl)pent-2-en-4-yn-1-ol
• 英文别名: (Z)-2-phenyl-5-trimethylsilanylpent-2-en-4-yn-1-ol；(Z)-2-phenyl-5-trimethylsilylpent-2-en-4-yn-1-ol
• CAS: 250358-91-9
• 化学式: C₁₄H₁₈OSi
• 分子量: 230.382
• InChiKey: HDMCDRZHVFUTGS-GXDHUFHOSA-N

物化性质

• 沸点：
  335.1±37.0 °C(Predicted)
• 密度：
  0.989±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.94
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  (Z)-2-phenyl-5-(trimethylsilyl)pent-2-en-4-yn-1-ol 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以93%的产率得到2-methyl-4-phenylfuran
  参考文献：
  名称：

  A General and Facile Synthesis of Substituted Furans by Palladium-Catalyzed Cycloisomerization of (Z)-2-En-4-yn-1-ols

  摘要：

  A general and facile synthesis of furans, based on Pd(II)-catalyzed cycloisomerization of (Z)-2-en-4-yn-1-ols, is described. Cycloisomerization reactions are carried out at 25-100 degrees C in the presence of a very simple catalytic system, consisting of K2PdI4, under essentially neutral conditions. This new methodology is very versatile and can be applied to the synthesis of a variety of substituted furans, including particularly fragile, naturally occurring furans such as rosefuran. Efficient synthetic approaches for the regioselective synthesis of suitably substituted (Z)-2-en-4-yn-1-ols have been developed.

  DOI：

  10.1021/jo990847h
• 作为产物：
  描述：

  苯基溴化镁 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 二乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 (Z)-2-phenyl-5-(trimethylsilyl)pent-2-en-4-yn-1-ol
  参考文献：
  名称：

  乙炔胺衍生的酮亚胺的分子内级联重排：获得无环和环状am

  摘要：

  乙炔胺与磺酰叠氮化物的铜催化反应提供了无环和环状am。在原位产生的酮亚胺上的链状氨基的亲核加成形成了六元环状两性离子中间体，其促进了链状氨基向C 5中心的迁移，从而得到了无环am。另一方面，氨基上的取代基向C 2-和C 4-中心的迁移导致形成环am。进行了计算研究以验证该机理，该机理表明该过程的产物分布取决于烯胺骨架上的取代。

  DOI：

  10.1039/c7ob00499k

文献信息

• Palladium-Catalyzed Oxidative Aminocarbonylation of Alkynols
  作者：Pierluigi Plastina、Bartolo Gabriele、Giuseppe Salerno

  DOI：10.1055/s-2007-983828

  日期：2007.10

  Alkynols undergo palladium-catalyzed aminocarbonylation leading to the direct formation of different heterocyclic derivatives, depending on the position of the OH group with respect to the triple bond. In the cases of 4-yn-1-ols and (Z)-2-en-4-yn-1-ols, the initially formed 2-ynamide intermediates, respectively, undergo cyclization leading to tetrahydrofuran derivatives or 2-furan-2-ylacetamides, respectively. In the case of 2-yn-1-ols, the aminocarbonylation products undergo intermolecular conjugate addition, followed by lactonization, leading to aminofuranones.

  炔醇在钯催化下进行氨基羰基化反应，根据羟基相对于三键的位置，可以直接形成不同的杂环衍生物。对于4-炔-1-醇和(Z)-2-烯-4-炔-1-醇，初始形成的2-炔酰胺中间体分别经历环化反应，分别生成四氢呋喃衍生物或2-呋喃-2-基乙酰胺。对于2-炔-1-醇，氨基羰基化产物经历分子间的共轭加成，随后进行内酯化，生成氨基呋喃酮。
• An Easy and Convenient Synthesis of 2-Furan-2-ylacetamides by Sequential Palladium-Catalyzed Oxidative Aminocarbonylation of (<i>Z</i>)-2-En-4-yn-1-ols/Conjugate Addition/Aromatization
  作者：Bartolo Gabriele、Pierluigi Plastina、Giuseppe Salerno、Raffaella Mancuso

  DOI：10.1055/s-2006-950360

  日期：——

  A simple and convenient synthesis of 2-furan-2-ylacet-amides 4 starting from readily available (Z)-2-en-4-yn-1-ols 1 is reported. The method is based on a PdI 2 -catalyzed oxidative aminocarbonylation of the triple bond of 1 to give the corresponding 2-ynamide intermediates 2, which undergo intramolecular conjugate addition to give 2-(5H-furan-2-ylidene)acetamide derivatives 3. Spontaneous or one-pot

  报道了一种从容易获得的 (Z)-2-en-4-yn-1-ols 1 开始的简单方便的 2-furan-2-ylacet-amides 4 合成方法。该方法基于 PdI 2 催化的 1 的三键氧化氨基羰基化，得到相应的 2-ynamide 中间体 2，其经过分子内共轭加成得到 2-(5H-furan-2-ylidene)acetamide 衍生物 3。 3 的自发或一锅酸促进芳构化最终导致最终的呋喃乙酰胺衍生物 4。
• An Efficient and General Synthesis of Furan-2-acetic Esters by Palladium-Catalyzed Oxidative Carbonylation of (<i>Z</i>)-2-En-4-yn-1-ols
  作者：Bartolo Gabriele、Giuseppe Salerno、Francesca De Pascali、Mirco Costa、Gian Paolo Chiusoli

  DOI：10.1021/jo990848+

  日期：1999.10.1

  A variety of (Z)-2-en-4-yn-1-ols have been carbonylated under oxidative conditions to give substituted furan-a-acetic esters in good yields. The cyclization-alkoxycarbonylation process occurs in alcoholic media at 50-70 degrees C and under 100 atm pressure of a 9:1 mixture of carbon monoxide and air in the presence of catalytic amounts of PdI2 in conjunction with KI. The proposed reaction pathway involves the in situ isomerization of the initially formed (E)-2-[(alkoxycarbonyl)methylene]-2,5-dihydrofuran species, which in some cases have been isolated and shown to be the intermediates.
• Intramolecular cascade rearrangements of enynamine derived ketenimines: access to acyclic and cyclic amidines
  作者：Dinesh Pratapsinh Chauhan、Sreejith J. Varma、Mahesh Gudem、Nihar Panigrahi、Khushboo Singh、Anirban Hazra、Pinaki Talukdar

  DOI：10.1039/c7ob00499k

  日期：——

  acyclic and cyclic amidines. Nucleophilic addition of the tethered amino group on the in situ generated ketenimine forms a six-membered cyclic zwitterionic intermediate which facilitates migration of the tethered amino group to the C5-center giving the acyclic amidine. On the other hand, migration of a substituent on the amino group to C2- and C4-centers results in the formation of cyclic amidines. Computational

  乙炔胺与磺酰叠氮化物的铜催化反应提供了无环和环状am。在原位产生的酮亚胺上的链状氨基的亲核加成形成了六元环状两性离子中间体，其促进了链状氨基向C 5中心的迁移，从而得到了无环am。另一方面，氨基上的取代基向C 2-和C 4-中心的迁移导致形成环am。进行了计算研究以验证该机理，该机理表明该过程的产物分布取决于烯胺骨架上的取代。
• A General and Facile Synthesis of Substituted Furans by Palladium-Catalyzed Cycloisomerization of (<i>Z</i>)-2-En-4-yn-1-ols
  作者：Bartolo Gabriele、Giuseppe Salerno、Egidio Lauria

  DOI：10.1021/jo990847h

  日期：1999.10.1

  A general and facile synthesis of furans, based on Pd(II)-catalyzed cycloisomerization of (Z)-2-en-4-yn-1-ols, is described. Cycloisomerization reactions are carried out at 25-100 degrees C in the presence of a very simple catalytic system, consisting of K2PdI4, under essentially neutral conditions. This new methodology is very versatile and can be applied to the synthesis of a variety of substituted furans, including particularly fragile, naturally occurring furans such as rosefuran. Efficient synthetic approaches for the regioselective synthesis of suitably substituted (Z)-2-en-4-yn-1-ols have been developed.