undec-1-en-5-yn-4-ol | 5186-02-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: undec-1-en-5-yn-4-ol
• CAS: 5186-02-7
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: PZUTZWMCGNPLAB-UHFFFAOYSA-N

物化性质

• 沸点：
  81-83 °C
• 密度：
  0.891±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 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：

  undec-1-en-5-yn-4-ol 在 18-冠醚-6 、 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 以93%的产率得到6-(hept-1-ynyl)-4-pentyl-5-vinyl-tetrahydro-2H-pyran-2-ol
  参考文献：
  名称：

  Control of Skeletal Connectivity in Indium Promoted Reactions:  1,2-Additions and Cope Rearrangements En Route to Lactol Formation

  摘要：

  Indium promoted coupling reactions between propargyl aldehydes (3) and allyl halides under aqueous and organic conditions are reported. Coupling reactions under aqueous conditions occur via 1,2-addition with excellent yields to afford 4-hydroxy-1-ene-5-ynes (8). Coupling reactions under organic conditions also add in a 1,2-fashion, but the initial products can be induced to undergo oxy-Cope rearrangements giving 2,5-hexadienals (9). Oxy-Cope rearrangement of 8 followed by a secondary addition step under highly basic conditions leads to lactol formation (10) in good to excellent yields. This paper reveals the versatility and control of product formation which may be attained when working with propargyl aldehyde (3) and allyl halide systems under indium promoted coupling conditions.

  DOI：

  10.1021/jo070020k
• 作为产物：
  描述：

  2-辛炔-1-醇 在 六甲基磷酰三胺 、 正丁基锂 、 1,10-菲罗啉 、 乙基溴化镁 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.0h， 生成 undec-1-en-5-yn-4-ol
  参考文献：
  名称：

  Radical cyclization of (bromomethyl)dimethylsilyl propargyl ethers. Regio-, chemo- and stereoselectivity.

  摘要：

  Radical cyclization of (bromomethyl)dimethylsilyl propargyl ether derivatives 1 is a powerful reaction with a high degree of regio-, chemo-, and stereoselectivity. Trisubstituted olefins 3, cyclopentene derivatives 5, and diquinane system 7j are obtained in good yields by a judicious choice of unsaturated substituents. Triquinane frameworks could be obtained stereoselectively from a suitable acyclic substrate of type 1 in a one-pot reaction. First attempts have not yet allowed us to aim at this goal due to interesting (1,5) hydrogen transfers. Moreover, we have intercepted, for the first time, the alpha-cyclopropyl radical which is involved in the Stork-Beckwith mechanism of the 5-versus 6-membered ring formation in the vinyl radical cyclization.

  DOI：

  10.1021/jo00037a026

文献信息

• Platinum- and Gold-Catalyzed Cycloisomerization Reactions of Hydroxylated Enynes
  作者：Victor Mamane、Tobias Gress、Helga Krause、Alois Fürstner

  DOI：10.1021/ja048094q

  日期：2004.7.1

  situ. This novel skeletal reorganization process was implemented into a concise total synthesis of the terpenes sabinone (18) and sabinol (19). Furthermore it is shown that conversion of the hydroxylated enynes into the corresponding acetates followed by reaction with a cationic gold catalyst formed from (PPh3)AuCl and AgSbF6 opens entry into isomeric products bearing the ketone function at the C-2

  在炔丙基位置之一含有羟基的烯炔暴露于催化量的 PtCl2 或 (PPh3)AuCl/AgSbF6 导致选择性重排，形成双环 [3.1.0] 己-3-酮衍生物。相同的产品是通过“一锅法”用烯丙基氯二甲基硅烷 (4) 和 PtCl 2 处理炔醛通过涉及初始铂催化烯丙基化的反应级联获得，然后是原位形成的高烯丙醇的环异构化。这种新颖的骨骼重组过程被实施到萜烯 sabinone (18) 和 sabinol (19) 的简明全合成中。此外，研究表明，羟基化的烯炔转化为相应的乙酸酯，然后与由 (PPh3)AuCl 和 AgSbF6 形成的阳离子金催化剂反应，打开进入在双环的 C-2 位置带有酮官能团的异构产物 [3.1 .0]己烷骨架。氘标记实验的结果和环异构化反应立体化学过程的分析与作为反应中间体的环丙基甲基铂卡宾物种的形成一致。
• Cyclic Alkenyl Boronic Half Acid Synthesis and Applications
  作者：LuAnne McNulty、Kris Kohlbacher、Katie Borin、Bryan Dodd、Jeni Bishop、Lindsey Fuller、Zach Wright

  DOI：10.1021/jo1003423

  日期：2010.9.3

  The synthesis of cyclic alkenyl boronic half acids from vinyl and propenyl boronic esters and homoallylic alcohols by ring-closing metathesis is reported. The method is compatible with both conventional and microwave heating and comparable yields are obtained under both conditions. The cyclic alkenyl boronic acids participate in Suzuki−Miyaura coupling reactions in good yields.

  报道了通过闭环复分解反应从乙烯基和丙烯基硼酸酯和均烯丙基醇合成环状烯基硼酸半酸。该方法与常规加热和微波加热均兼容，并且在两种条件下均获得了相当的产率。环状烯基硼酸以良好的产率参与Suzuki-Miyaura偶联反应。
• Cr-waste free catalytic carbonyl addition reactions with polymer-immobilized CrF2
  作者：Michio Kurosu

  DOI：10.1016/j.tetlet.2006.03.071

  日期：2006.5

  A monomeric [Cr(pyridine)(4)F-2]Br-+(-) is immobilized onto the dipyridyl-TentaGel resin. Allylations of aldehydes with 5-10 mol % of the CrF2-dipyridyi-TentaGel resin 2/Mn/TMSCl in THF provide the corresponding homoallylic alcohols in excellent yields after TMS-desilylations with a polymer-supported ammonium fluoride 3. The recovered CrF2-dipyridyi-TentaGel resins can be utilized multiple times without a decrease of reactivity. (c) 2006 Elsevier Ltd. All rights reserved.
• Gaudemar,M.; Travers,S., Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques, 1966, vol. 262, p. 139 - 141
  作者：Gaudemar,M.、Travers,S.

  DOI：——

  日期：——
• Control of Skeletal Connectivity in Indium Promoted Reactions:  1,2-Additions and Cope Rearrangements En Route to Lactol Formation
  作者：Thomas Mitzel、Joe Wzorek、Annie Troutman、Kristen Allegue

  DOI：10.1021/jo070020k

  日期：2007.4.1

  Indium promoted coupling reactions between propargyl aldehydes (3) and allyl halides under aqueous and organic conditions are reported. Coupling reactions under aqueous conditions occur via 1,2-addition with excellent yields to afford 4-hydroxy-1-ene-5-ynes (8). Coupling reactions under organic conditions also add in a 1,2-fashion, but the initial products can be induced to undergo oxy-Cope rearrangements giving 2,5-hexadienals (9). Oxy-Cope rearrangement of 8 followed by a secondary addition step under highly basic conditions leads to lactol formation (10) in good to excellent yields. This paper reveals the versatility and control of product formation which may be attained when working with propargyl aldehyde (3) and allyl halide systems under indium promoted coupling conditions.