3-methyl-5-phenylpent-1-en-4-yn-3-ol | 26644-92-8

• 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: 3-methyl-5-phenylpent-1-en-4-yn-3-ol
• CAS: 26644-92-8
• 化学式: C₁₂H₁₂O
• 分子量: 172.227
• InChiKey: GYQSNHQHWVUKNL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  3-methyl-5-phenylpent-1-en-4-yn-3-ol 生成 trimethyl((3-methyl-5-phenylpent-1-en-4-yn-3-yl)oxy)silane
  参考文献：
  名称：

  Reactivity of 3-silyloxy-1,4-enynes: Gold(III)-catalyzed regioselective nucleophilic substitution

  摘要：

  Gold-catalyzed reactions of 3-silyloxy-1,4-enynes with alcohols afford primary, secondary, and tertiary pent-2-en-4-ynyl ethers in moderate to excellent yields. The substitution proceeds with high regioselectivity. An initial cyclization providing five-membered carbocycles instead was not observed under the reaction conditions. Control experiments show that these reactions are also catalyzed by Bronsted- and Lewis-acids, although scope and yields are markedly reduced. (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.09.062
• 作为产物：
  描述：

  丁烯酮 、 lithium phenylacetylide 生成 3-methyl-5-phenylpent-1-en-4-yn-3-ol
  参考文献：
  名称：

  Reactivity of 3-silyloxy-1,4-enynes: Gold(III)-catalyzed regioselective nucleophilic substitution

  摘要：

  Gold-catalyzed reactions of 3-silyloxy-1,4-enynes with alcohols afford primary, secondary, and tertiary pent-2-en-4-ynyl ethers in moderate to excellent yields. The substitution proceeds with high regioselectivity. An initial cyclization providing five-membered carbocycles instead was not observed under the reaction conditions. Control experiments show that these reactions are also catalyzed by Bronsted- and Lewis-acids, although scope and yields are markedly reduced. (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.09.062

文献信息

• Stereospecific Decarboxylative Nazarov Cyclization Mediated by Carbon Dioxide for the Preparation of Highly Substituted 2-Cyclopentenones
  作者：Keiichi Komatsuki、Yuta Sadamitsu、Kohei Sekine、Kodai Saito、Tohru Yamada

  DOI：10.1002/anie.201705909

  日期：2017.9.11

  Highly substituted 2‐cyclopentenones were stereospecifically and regioselectively constructed with high catalytic efficiency through Lewis‐acid catalyzed decarboxylative Nazarov cyclization of the cyclic carbonate derivative, which is prepared by reacting the propargyl alcohol with carbon dioxide in the presence of a silver catalyst. The stereochemistry of the 2‐cyclopentenone is strictly controlled

  通过路易斯酸催化的环状碳酸酯衍生物的脱羧纳扎罗夫环化反应，以高催化效率立体选择性和区域选择性地构建了高度取代的2-环戊烯酮，环状碳酸酯衍生物是通过使炔丙基醇与二氧化碳在银催化剂存在下反应制备的。2-环戊烯酮的立体化学严格受起始材料中烯烃的几何形状控制。该方法适用于各种基板。
• General and Regioselective Synthesis of Substituted Pyrroles by Metal-Catalyzed or Spontaneous Cycloisomerization of (<i>Z</i>)-(2-En-4-ynyl)amines
  作者：Bartolo Gabriele、Giuseppe Salerno、Alessia Fazio

  DOI：10.1021/jo034850j

  日期：2003.10.1

  A general and regioselective synthesis of substituted pyrroles 2 by cycloisomerization of readily available (Z)-(2-en-4-ynyl)amines 1 is reported. Spontaneous cycloisomerization leading to 2 occurred in the course of preparation of enynamines bearing a terminal triple bond or a triple bond substituted with a phenyl or a CH2OTHP group. When the triple bond was substituted with an alkyl or alkenyl group

  据报道，通过容易获得的（Z）-（2-en-4-炔基）胺1的环异构化，一般和区域选择性地合成取代的吡咯2。在制备带有末端三键或被苯基或CH 2 OTHP基团取代的三键的烯胺的过程中发生自发的环异构化反应，导致2。当三键被烷基或烯基取代时，烯胺是稳定的并且可以通过金属催化转化为相应的吡咯。发现CuCl2是用于在C-3处取代的底物进行环异构化的出色催化剂，而PdX2与KX（X = Cl，I）结合使用则是在C-3处未取代的烯胺反应的优良催化剂。
• Pd-Catalyzed Enantioselective (3+2)-Cycloaddition of Vinyl-Substituted Oxyallyl Carbonates with Isocyanates and Ketones
  作者：Xuemei Pan、Limei Yu、Simin Wang、Rui Wu、Chunyan Ou、Minghui Xu、Bin Chen、Yuanji Gao、Hai-Liang Ni、Ping Hu、Bi-Qin Wang、Peng Cao

  DOI：10.1021/acs.orglett.2c00290

  日期：2022.3.25

  C,O-dipole for enantioselective Pd-catalyzed (3+2) cycloaddition. The corresponding oxyallyl-Pd species was weakly nucleophilic to react with activated carbonyl compounds, affording multisubstituted and enantioenriched oxazolidinones and 1,3-dioxolanes with a high degree of chemo- and stereoselectivity. The synthetic transformations of oxazolidinone product were carried out to build enantioenriched

  乙烯基取代的碳酸氧烯丙酯被用作一种新的 C,O-偶极子，用于对映选择性 Pd 催化的 (3+2) 环加成反应。相应的 oxyallyl-Pd 物质具有弱亲核性，可与活性羰基化合物反应，从而提供具有高度化学和立体选择性的多取代和对映体富集的恶唑烷酮和 1,3-二氧戊环。对恶唑烷酮产物进行合成转化以构建对映体富集的α-手性氨基酮和环氧衍生物。
• Novel Synthesis of Substituted Thiophenes by Palladium-Catalyzed Cycloisomerization of (<i>Z</i>)-2-En-4-yne-1-thiols
  作者：Bartolo Gabriele、Giuseppe Salerno、Alessia Fazio

  DOI：10.1021/ol991297c

  日期：2000.2.1

  [reaction: see text] The first example of palladium-catalyzed cycloisomerization of (Z)-2-en-4-yne-1-thiols 1 to give substituted thiophenes 2 is reported. Cycloisomerization reactions are carried out under nitrogen at 25-100 degrees C in N,N-dimethylacetamide as the solvent in the presence of catalytic amounts of PdI2 in conjunction with KI to give the corresponding thiophenes in 43-94% yield.

  [反应：见正文]报告了钯催化的（Z）-2-en-4-yne-1-thiols 1的环异构化反应，得到取代的噻吩2的第一个例子。在催化量的PdI2和KI存在下，在氮气，25-100℃，N，N-二甲基乙酰胺为溶剂的条件下，进行环异构化反应，得到相应的噻吩，收率为43-94％。
• Development of an Anomalous Heck Reaction:  Skeletal Rearrangement of Divinyl and Enyne Carbinols
  作者：J. Maina Ndungu、Kimberly K. Larson、Richmond Sarpong

  DOI：10.1021/ol052382p

  日期：2005.12.1

  [reaction: see text] A general set of conditions that achieves the union of aryl halides and divinyl or enyne carbinols to afford tri- or tetrasubstituted olefins in good yields (up to 83%) is described. The mechanism by which this proceeds is believed to involve the intermediacy of a cyclopropanol, followed by a novel skeletal reorganization. The ability to suppress beta-hydride elimination of organopalladium

  [反应：见正文] 描述了实现芳基卤化物与二乙烯基或烯炔醇结合以以良好产率（高达 83%）提供三取代或四取代烯烃的一组通用条件。据信，这一过程的机制涉及环丙醇的中介作用，然后是新的骨架重组。抑制有机钯中间体的β-氢化物消除的能力似乎对于这些过程的成功至关重要。