3-(trimethylsilylethynyl)-2-cyclohexen-1-one | 124267-25-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(trimethylsilylethynyl)-2-cyclohexen-1-one
• 英文别名: 3-[(Trimethylsilyl)ethynyl]cyclohex-2-en-1-one；3-(2-trimethylsilylethynyl)cyclohex-2-en-1-one
• CAS: 124267-25-0
• 化学式: C₁₁H₁₆OSi
• 分子量: 192.333
• InChiKey: HIGCZGKLLBSVTF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.55
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 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：

  3-(trimethylsilylethynyl)-2-cyclohexen-1-one 在 potassium fluoride 、 苄基三乙基氯化铵 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以92%的产率得到3-ethynyl-2-cyclohexen-1-one
  参考文献：
  名称：

  NHC催化苯甲醛系链与环烯酮的分子内固结反应构建螺旋稠合三环骨架

  摘要：

  由市售的2-羟基苯甲醛通过三步法，包括三氟甲磺酸盐的形成，Sonogashira交叉偶联和区域选择性氢化来制备具有环烯酮的各种苯甲醛系链。然后将这些底物暴露于N-杂环卡宾，随后分子内Stetter反应顺利进行，以30-87％的收率得到各种螺旋稠合的三环1,4-二酮。在Stetter条件下，呋喃醛和烟醛衍生物也参与了该反应。

  DOI：

  10.1021/acs.joc.9b01403
• 作为产物：
  描述：

  3-乙氧基-2-环己烯-1-酮 在 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 24.0h， 生成 3-(trimethylsilylethynyl)-2-cyclohexen-1-one
  参考文献：
  名称：

  Synthesis and Evaluation of Novel α-Fluorinated (E)-3-((6-Methylpyridin-2-yl)ethynyl)cyclohex-2-enone-O-methyl Oxime (ABP688) Derivatives as Metabotropic Glutamate Receptor Subtype 5 PET Radiotracers

  摘要：

  In the search for an optimal fluorine-18-labeled positron emission tomography (PET) radiotracer for imaging metabotropic glutamate receptor subtype 5 (mGluRS), we have prepared a series of five alpha-fluorinated derivatives based on the ABP688 structural manifold by application of a two-step enolization/NFSI a-fluorination method. Their binding affinities were evaluated in vitro, and the most promising candidate (Z)-16 exhibited a K-i of 5.7 nM and a clogP value of 2.3. The synthesis of the precursor tosylate (E)-22 revealed a preference for the (E)-configurational isomer (K-i = 31.2 nM), and successful radiosynthesis afforded (E)-[F-18]-16 which was used as a model PET tracer to establish plasma and PBS stability. (E)-[F-18]-16 (K-d = 70 nM) exhibited excellent specificity for mGluRS in autoradiographic studies on horizontal rat brain slices in vitro.

  DOI：

  10.1021/jm300648b

文献信息

• Formation of Quaternary Stereogenic Centers by NHC-Cu-Catalyzed Asymmetric Conjugate Addition Reactions with Grignard Reagents on Polyconjugated Cyclic Enones
  作者：Matthieu Tissot、Daniele Poggiali、Hélène Hénon、Daniel Müller、Laure Guénée、Marc Mauduit、Alexandre Alexakis

  DOI：10.1002/chem.201200502

  日期：2012.7.9

  The copper‐catalyzed conjugate addition of various Grignard reagents to polyconjugated enones (dienone and enynone derivatives) is reported. The catalyst system, composed of copper triflate and an NHC ligand, led to the unusual selective formation of the 1,4‐addition products. This reaction allows for the creation of all‐carbon chiral quaternary centers with enantiomeric excesses up to 99 %. The remaining

  据报道，各种格氏试剂在铜催化下将共轭加成物加到共轭烯酮（二烯酮和烯酮衍生物）上。由三氟甲磺酸铜和NHC配体组成的催化剂体系导致1,4加成产物的异常选择性形成。该反应可以创建对映异构体过量高达99％的全碳手性四元中心。1,4加合物上剩余的不饱和基团使您可以进行有价值的合成转化。
• Highly Enantioselective and Regioselective Copper-Catalyzed 1,4 Addition of Grignard Reagents to Cyclic Enynones
  作者：Matthieu Tissot、Alexandra Pérez Hernández、Daniel Müller、Marc Mauduit、Alexandre Alexakis

  DOI：10.1021/ol200219m

  日期：2011.3.18

  regioselectivity with respect to copper-catalyzed conjugate additions of various Grignard reagents to cyclic enynones. The use of Cu(OTf)2 and NHC ligand L1 as the catalyst combination in CH2Cl2 led to the unique formation of the 1,4 adduct. This selectivity does not follow the general trend previously observed in the literature using extended Michael acceptors. Moreover these reactions allowed for the creation

  在这封信中，我们描述了相对于铜催化的各种格氏试剂向环烯酮的铜催化共轭加成的区域选择性方面的不同寻常的结果。Cu（OTf）2和NHC配体L1作为CH 2 Cl 2中的催化剂组合的使用导致1,4加合物的独特形成。这种选择性不符合以前使用扩展的迈克尔受体在文献中观察到的一般趋势。此外，这些反应允许建立具有高达97％ee的对映选择性的四元立体学中心。
• Two methods for the preparation of 2-cyclohexenones from resin-bound 1,3-cyclohexanedione
  作者：Mark E. Fraley、Robert S. Rubino

  DOI：10.1016/s0040-4039(97)00631-x

  日期：1997.5

  The addition of organolithium or Grignard reagents to vinylogous ester resin 1 followed by mild hydrolysis of product resins 2 provides 3-alkyl-2-cyclohexenones in high purity (>95%). Alternatively, conversion of 1 to vinyl triflate resin 4 followed by palladium-mediated couplings with aryl boronic acids and hydrolysis furnishes 3-aryl-2-cyclohexenones in lower yield, but exceptional purity.

  将有机锂或格氏试剂添加到乙烯基酯树脂1中，然后产物树脂2的温和水解提供了高纯度（＞ 95％）的3-烷基-2-环己烯酮。或者，将1转化为三氟甲基丙烯酸酯树脂4，然后与芳基硼酸进行钯介导的偶联并水解，从而以较低的收率提供了3-芳基-2-环己酮，但纯度却很高。
• A copper-free palladium catalyzed cross coupling reaction of vinyl tosylates with terminal acetylenes
  作者：Xiaoyong Fu、Shuyi Zhang、Jianguo Yin、Doris P. Schumacher

  DOI：10.1016/s0040-4039(02)01447-8

  日期：2002.9

  A copper-free palladium-catalyzed cross coupling of vinyl tosylate (2) and terminal acetylenes was investigated, affording a convenient and efficient method for construction of an sp–sp2 carboncarbon bond. The tosylate (2) derived from 1,3-cyclohexanedione was reacted with terminal acetylene under the copper-free conditions at ambient temperature, in the presence of palladium acetate and triphenylphosphine

  研究了无铜钯催化的甲苯磺酸乙烯酯（2）与末端乙炔的交叉偶联，为构建sp - sp 2碳碳键提供了一种方便而有效的方法。在乙酸铜和三苯膦的存在下，在室温下在无铜条件下，将衍生自1,3-环己二酮的甲苯磺酸酯（2）与末端乙炔进行反应，从而以优异的总收率提供共轭的烯炔产物。同时保留其他功能组不变。该反应方案扩展至香豆素甲苯磺酸酯（12）。
• Stereoselective synthesis of exocyclic allenes by double hydride reduction of 3-alkynyl-2-cycloalkenones
  作者：Matthew A. Gubbels、Martin Hulce、John M. Kum、Andrew K. Urick、Eric M. Villa

  DOI：10.1016/j.tet.2016.07.058

  日期：2016.10

  Exocyclic allene natural products and pharmaceutical agents are rare but interesting compounds: Fucoxanthin, grasshopper ketone, and analogues of prostacyclins, cephalosporins, antithrombic agents and sterol biosynthesis inhibitors are representative. Syntheses of exocyclic allenes commonly rely on extended conjugate additions to e.g., alk-2-en-4-ynones, syn SN2′-like additions to alkynyl oxiranes

  环外丙二烯天然产物和药物是稀有但有趣的化合物：褐藻黄质，蚱酮和前列环素，头孢菌素，抗血栓剂和固醇生物合成抑制剂的类似物是代表性的。环外烯丙基的合成通常依赖于扩展的共轭加成，例如，alk-2-en-4-ynones，syn S N炔基肟基的2'样加成，以及炔丙基硅烷的亲电取代等取代反应。我们报告说3-炔基-2-环烯酮与2当量的各种氢铝酸盐而不是氢硼酸盐的反应是通过非对映选择性的1,4-还原乙烯基炔丙基中间体醇盐进行的，以提供环外烯丙基为主要产物。还观察到异构的3-炔基环烷醇。