diethyl 2-(3-phenylprop-2-yn-1-yl)-2-(3-(trimethylsilyl)prop-2-yn-1-yl)malonate

• 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: diethyl 2-(3-phenylprop-2-yn-1-yl)-2-(3-(trimethylsilyl)prop-2-yn-1-yl)malonate
• 英文别名: Diethyl 2-(3-phenylprop-2-ynyl)-2-(3-trimethylsilylprop-2-ynyl)propanedioate
• 化学式: C₂₂H₂₈O₄Si
• 分子量: 384.547
• InChiKey: VMKNCDPUNZAISY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.81
• 重原子数：
  27
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl 2-(3-phenylprop-2-yn-1-yl)-2-(3-(trimethylsilyl)prop-2-yn-1-yl)malonate 在 四丁基氟化铵 、 1,2-双(二苯基膦)乙烷 、 cobalt(II) chloride 、 锌 作用下， 以 四氢呋喃 、 N-甲基吡咯烷酮 、 二甲基亚砜 为溶剂， 反应 32.0h， 生成 3-methyl-1-phenyl-5,7-dihydro-[2]pyrindine-6,6-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  On-Demand Generation of an Efficient Catalyst for Pyridine Formation from Unactivated Nitriles and α,ω-Diynes Using CoCl₂-6H₂O, dppe, and Zn

  摘要：

  A highly practical, general method for catalytic formation of substituted pyridines from a variety of unactivated nitriles and alpha,omega-diynes is given. The reactions which were catalyzed by 5 mol % of dppe/CoCl2-6H(2)O in the presence of Zn powder (10 mol %) could proceed at rt to similar to 50 degrees C with high functional compatibility and regioselectivity.

  DOI：

  10.1021/ol070037p
• 作为产物：
  描述：

  diethyl 2-(3-phenylprop-2-yn-1-yl)malonate 在 正丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 、 mineral oil 为溶剂， 反应 15.0h， 生成 diethyl 2-(3-phenylprop-2-yn-1-yl)-2-(3-(trimethylsilyl)prop-2-yn-1-yl)malonate
  参考文献：
  名称：

  Diols, α-Ketols, and Diones as 2_2π Components in [2+2+2] Cycloadditions of 1,6-Diynes via Ruthenium(0)-Catalyzed Transfer Hydrogenation

  摘要：

  The first use of vicinal diols, ketols, or diones as 2(2 pi) components in metal-catalyzed [2+2+2] cycloaddition is described. Using ruthenium(0) catalysts, 1,6-diynes form ruthenacyclopentadienes that engage transient diones in successive carbonyl addition. Transfer hydrogenolysis of the resulting ruthenium(II) diolate mediated by the diol or ketol reactant releases the cycloadduct with regeneration of ruthenium(0) and the requisite dione.

  DOI：

  10.1021/jacs.6b11746

文献信息

• Regioselective Syntheses of Substituted Pyridines and 2,2′-Bipyridines by Cobalt-Catalyzed [2+2+2] Cycloaddition of α,ω-Diynes with Nitriles
  作者：Sentaro Okamoto、Yu-ki Sugiyama

  DOI：10.1055/s-0030-1260068

  日期：2011.7

  2-bis(diphenylphosphino)ethane-cobalt(II) chloride-zinc catalyst in 1-methylpyrrolidin-2-one at room temperature to 50 ˚C, α,ω-diynes reacted with nitriles by a [2+2+2] cycloaddition pathway to give annulated pyridines or 2,2′-bipyridines. The regioselectivity of the reaction is controlled by a combination of steric and electronic effects. The reaction of diynes with a terminal trimethylsilyl group gave the

  在室温至50℃下，在1-甲基吡咯烷-2-酮中存在1,2-双（二苯基膦基）乙烷-氯化钴（II）-锌催化剂时，α，ω-二炔与腈通过[ 2 + 2 + 2]环加成途径得到环状吡啶或2,2'-联吡啶。反应的区域选择性由空间效应和电子效应的组合来控制。二炔与末端三甲基甲硅烷基的反应仅给出了相应的3-（三甲基甲硅烷基）吡啶。这些产物可以被原甲硅烷基化或卤代甲硅烷基化，得到相应的质子化或卤化吡啶或2,2'-联吡啶。 环加成-杂环-均相催化-吡啶-区域选择性
• Ruthenium-Catalyzed Transfer Oxygenative [2 + 2 + 1] Cycloaddition of Silyldiynes Using Nitrones as Adjustable Oxygen Atom Donors. Synthesis of Bicyclic 2-Silylfurans
  作者：Kazuma Matsui、Masatoshi Shibuya、Yoshihiko Yamamoto

  DOI：10.1021/acscatal.5b01855

  日期：2015.11.6

  The first example of the Ru-catalyzed transfer oxygenative [2 + 2 + 1] cycloaddition of silyldiynes to produce bicyclic 2-silylfurans is described. This cyclization process was realized using nitrones as readily available and adjustable oxygen atom donors. The bicyclic silylfuran products could be used as platforms for a diverse range of functionalized furans.
• Diols, α-Ketols, and Diones as 2_2π Components in [2+2+2] Cycloadditions of 1,6-Diynes via Ruthenium(0)-Catalyzed Transfer Hydrogenation
  作者：Hiroki Sato、Matthias Bender、Weijie Chen、Michael J. Krische

  DOI：10.1021/jacs.6b11746

  日期：2016.12.21

  The first use of vicinal diols, ketols, or diones as 2(2 pi) components in metal-catalyzed [2+2+2] cycloaddition is described. Using ruthenium(0) catalysts, 1,6-diynes form ruthenacyclopentadienes that engage transient diones in successive carbonyl addition. Transfer hydrogenolysis of the resulting ruthenium(II) diolate mediated by the diol or ketol reactant releases the cycloadduct with regeneration of ruthenium(0) and the requisite dione.
• On-Demand Generation of an Efficient Catalyst for Pyridine Formation from Unactivated Nitriles and α,ω-Diynes Using CoCl₂-6H₂O, dppe, and Zn
  作者：Kouki Kase、Avijit Goswami、Kazuhiko Ohtaki、Emi Tanabe、Naoko Saino、Sentaro Okamoto

  DOI：10.1021/ol070037p

  日期：2007.3.1

  A highly practical, general method for catalytic formation of substituted pyridines from a variety of unactivated nitriles and alpha,omega-diynes is given. The reactions which were catalyzed by 5 mol % of dppe/CoCl2-6H(2)O in the presence of Zn powder (10 mol %) could proceed at rt to similar to 50 degrees C with high functional compatibility and regioselectivity.