2-prop-2-ynylcyclopentanone | 19842-40-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-prop-2-ynylcyclopentanone
• 英文别名: 2-propargylcyclopentanone；2-Propargyl-cyclopentanon；2-(Prop-2-yn-1-yl)cyclopentan-1-one；2-prop-2-ynylcyclopentan-1-one
• CAS: 19842-40-1
• 化学式: C₈H₁₀O
• 分子量: 122.167
• InChiKey: CLPCXIOMHWOYBD-UHFFFAOYSA-N

物化性质

• 沸点：
  76-77 °C(Press: 12 Torr)
• 密度：
  0.992±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-prop-2-ynylcyclopentanone 在 镍 sodium hydroxide 、 sodium tetrahydroborate 、 氢气 作用下， 以 乙醇 为溶剂， 生成 (+/-)-1r-propyl-cyclopentanol-(2t)
  参考文献：
  名称：

  Substituted acetylenes. LXXXVIII. Alkylation of enamines with tert-propargylic acid chlorides

  摘要：

  DOI：

  10.1021/jo00834a041
• 作为产物：
  描述：

  3-(2-氧代环戊基)丙醛 在 全氟丁基磺酰氟 、 (叔丁基亚氨基)三(吡咯烷)膦 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 2-prop-2-ynylcyclopentanone
  参考文献：
  名称：

  Convenient synthesis of non-conjugated alkynyl ketones from keto aldehydes by a chemoselective one-pot nonaflation—base catalyzed elimination sequence

  摘要：

  Keto aldehydes were selectively converted to non-conjugated alkynyl ketones possessing an unsubstituted alkyne terminus using one-pot nonaflation-base catalyzed elimination reaction sequences. Consecutive one-pot nonaflation of keto aldehydes with perfluorobutane-l-sulfonyl fluoride and elimination of the nonaflyl group using the P(1) phosphazene base resulted in the formation of a terminal C C triple bond with the keto group remaining intact. Careful optimization of the reaction conditions enabled a highly chemoselective conversion of the aldehyde function in the presence of unprotected keto groups exploiting a minor difference in acidity of their alpha-hydrogen atoms. Scope and limitations of the protocol as well as possible implementation of these substrates in Sonogashira coupling were explored. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.05.095

文献信息

• Gold-Catalyzed 1,3-Acyloxy Migration/5-exo-dig Cyclization/1,5-Acyl Migration of Diynyl Esters
  作者：David Lebœuf、Antoine Simonneau、Corinne Aubert、Max Malacria、Vincent Gandon、Louis Fensterbank

  DOI：10.1002/anie.201101179

  日期：2011.7.18

  Working three shifts: Polyconjugated δ‐diketones are formed stereoselectively in high yields by the gold‐catalyzed rearrangement of 1,6‐diyn‐3‐yl esters. This cascade involves a 1,3‐sigmatropic acyloxy shift, a 5‐exo‐dig cyclization of the resulting allenyne, and an unprecedented 1,5‐sigmatropic shift of an acyl fragment. The usefulness of the products was shown by an efficient acid‐catalyzed transformation

  进行三班制：通过金催化的1,6-二炔基-3-基酯的重排，高收率立体选择性地形成了多共轭δ-二酮。这种级联反应涉及1,3-σ的酰氧基转移，所得烯丙炔的5- exo- dig环化反应以及酰基片段前所未有的1,5-σ的转移。有效的酸催化转化为复杂的多环骨架表明了产品的实用性。
• Synthesis of Exo- and Endocyclic Enamides Through Copper-Catalyzed Regioselective Intramolecular <i>N</i> -Halovinylation
  作者：Nicolas Gilbert、Simon Ricard、Jodrey Bergeron、Pierre Lambolez、Benoit Daoust

  DOI：10.1002/ejoc.202000137

  日期：2020.5.10

  copper‐catalyzed cross‐coupling of 1,2‐dihaloalkenes and amides leads to cyclic β‐haloenamides, which can participate in a second cross‐coupling reaction to efficiently synthesize highly functionalized cyclic enamides. The selectivity of the intramolecular coupling between exo‐ and endocyclic regioisomers is a crucial synthetic factor and can be influenced by the structure of the substrate and the reaction conditions

  1,2-二卤代烯烃与酰胺的分子内铜催化交叉偶联反应生成环状β-卤代烯酰胺，后者可参与第二次交叉偶联反应以有效合成高度官能化的环状酰胺。外环和内环区域异构体之间分子内偶联的选择性是至关重要的合成因素，并受底物结构和反应条件的影响。
• Silver-Free Activation of Ligated Gold(I) Chlorides: The Use of [Me₃NB₁₂Cl₁₁]⁻as a Weakly Coordinating Anion in Homogeneous Gold Catalysis
  作者：Michael Wegener、Florian Huber、Christoph Bolli、Carsten Jenne、Stefan F. Kirsch

  DOI：10.1002/chem.201404487

  日期：2015.1.12

  Phosphane and N‐heterocyclic carbene ligated gold(I) chlorides can be effectively activated by Na[Me3NB12Cl11] (1) under silver‐free conditions. This activation method with a weakly coordinating closo‐dodecaborate anion was shown to be suitable for a large variety of reactions known to be catalyzed by homogeneous gold species, ranging from carbocyclizations to heterocyclizations. Additionally, the

  在无银条件下，Na [Me 3 NB 12 Cl 11 ]（1）可以有效活化磷化氢和N-杂环卡宾相连的氯化金（I）。这种具有弱配位的活化方法闭合碳-dodecaborate阴离子被证明是适合于大量的各种已知由均匀的金物种催化的反应，从carbocyclizations到heterocyclizations的。此外，还证明了1在以前未知的5-甲硅烷氧基-1,6-炔烃转化中的能力。
• Synergistic Catalysis: Metal/Proton-Catalyzed Cyclization of Alkynones Toward Bicyclo[3.<i>n</i>.1]alkanones
  作者：Shifa Zhu、Qiaohui Zhang、Kai Chen、Huanfeng Jiang

  DOI：10.1002/anie.201504964

  日期：2015.8.3

  highly efficient and practical synergistically metal/proton‐catalyzed Conia–ene reaction for the synthesis of bicyclo[3.n.1]alkanones has been developed. This synergistic catalysis was successfully utilized in modifying natural compounds such as methyl dihydrojasmonate, α,β‐thujone, and 5α‐cholestan‐3‐one. Furthermore, the bridged carbonyl group of bicyclo[3.2.1]alkanones could be easily attacked by nucleophiles

  已开发出一种高效且实用的协同金属/质子催化的Conia-ene反应合成双环[3.n.1]烷酮。这种协同催化作用已成功用于修饰天然化合物，例如二氢茉莉酮酸甲酯，α，β-thujone和5α-cholestan-3-one。此外，亲核试剂很容易攻击双环[3.2.1]链烷酮的桥连羰基，从而以优异的收率得到开环的环庚烯酮产物或双环[4.2.1]酰胺。这些反应提供了从简单的起始原料或天然存在的化合物快速进入各种环状结构的途径。
• Tandem Anionic 5-Exo Dig Cyclization/Claisen Rearrangement as an Efficient Route to Fused Polycyclic Ring Systems
  作者：Timo V. Ovaska、Jonathan B. Roses

  DOI：10.1021/ol006139w

  日期：2000.7.1

  The scope and limitations of a tandem 5-exo dig cyclization/Claisen rearrangement sequence involving appropriately substituted 4-alkyn-1-ols as an efficient "one-pot" route to fused tricyclic ring systems is described. The reaction rates were found to be strongly dependent on the nature of the terminal substitutent of the triple bond. In some cases the entire sequence was found to proceed in good yield

  描述了串联5-exo dig环化/ Claisen重排序列的范围和局限性，其中涉及适当取代的4-炔-1-醇作为通往稠合三环系统的有效“一锅”路线。发现反应速率强烈依赖于三键的末端取代基的性质。在某些情况下，发现整个序列在低至115摄氏度的温度下都能以良好的产率进行。