diethyl 2-allyl-2-(3-(trimethylsilyl)prop-2-yn-1-yl)malonate | 113281-31-5

• 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-allyl-2-(3-(trimethylsilyl)prop-2-yn-1-yl)malonate
• 英文别名: diethyl 1-(trimethylsilyl)-6-hepten-1-yne-4,4-dicarboxylate；Diethyl 2-prop-2-enyl-2-(3-trimethylsilylprop-2-ynyl)propanedioate
• CAS: 113281-31-5
• 化学式: C₁₆H₂₆O₄Si
• 分子量: 310.466
• InChiKey: ARGJTUHUTQTUDA-UHFFFAOYSA-N

物化性质

• 沸点：
  337.3±42.0 °C(Predicted)
• 密度：
  0.989±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.95
• 重原子数：
  21
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 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-allyl-2-(3-(trimethylsilyl)prop-2-yn-1-yl)malonate 在 palladium on activated charcoal 一氯化碘 、 sodium carbonate 作用下， 以 乙二醇二甲醚 、 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 12.0h， 生成 5-oxo-6-phenyl-3,3a,4,5-tetrahydro-1H-pentalene-2,2-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  Practical and Efficient Suzuki−Miyaura Cross-Coupling of 2-Iodocycloenones with Arylboronic Acids Catalyzed by Recyclable Pd(0)/C

  摘要：

  The first Suzuki-Miyaura cross-coupling of 2-iodocycloenones with arylboronic acids catalyzed by 10% Pd(O)/C is described as an interesting alternative to classical homogeneous conditions. Most of the substrate reacted under mild condition at 25 degrees C under air in aqueous DME. The conditions described tolerate a wide range of iodoenones and boronic acids. Notably, the procedure features inexpensive reagents and solvents with low toxicity rendering the method environmentally benign. Additionally 10% Pd(O)/C could be recovered and efficiently reused at least five times without significant alteration of the yields of the cross-coupled product.

  DOI：

  10.1021/jo051501b
• 作为产物：
  描述：

  三甲硅基丙炔醇 在 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 diethyl 2-allyl-2-(3-(trimethylsilyl)prop-2-yn-1-yl)malonate
  参考文献：
  名称：

  The rhodium-catalyzed Pauson–Khand reaction

  摘要：

  A rhodium carbonyl complex, [RhCl(CO)(2)](2), serves as a catalyst of the intra- and inter-molecular Pauson-Khand reaction. By the use of the rhodium catalyst, cyclopentenone derivatives are prepared from various 1,6- and 1,7-enynes under 1 arm of CO. Furthermore, this rhodium-catalyzed reaction is accelerated by reducing partial pressure of CO to less than 1 atm. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00835-4

文献信息

• Catalytic Generation of Rhodium Silylenoid for Alkene–Alkyne–Silylene [2 + 2 + 1] Cycloaddition
  作者：Toshimichi Ohmura、Ikuo Sasaki、Michinori Suginome

  DOI：10.1021/acs.orglett.9b00326

  日期：2019.3.15

  2 + 1] cycloaddition takes place in the rhodium-catalyzed reaction of 1,6-enynes with borylsilanes bearing an alkoxy group on the silicon atoms, which react as synthetic equivalents of silylene. The reaction proceeds efficiently in 1,2-dichloroethane at 80–110 °C in the presence of a rhodium catalyst bearing bis(diphenylphosphino)methane (DPPM) as a ligand to afford 1-silacyclopent-2-enes in good to

  烯烃-炔烃-亚甲基[2 + 2 +1]的环加成反应是在铑催化的1,6-炔烃与在硅原子上带有烷氧基的硼烷基硅烷的反应中进行的，这些硅烷作为合成的甲硅烷基等效物进行反应。在载有双（二苯基膦基）甲烷（DPPM）作为配体的铑催化剂存在下，反应在80-110°C的1,2-二氯乙烷中有效进行，从而以高收率或高收率得到1-silacyclopent-2-enes。
• Stereoselective Nickel-Catalyzed [2+2+2] Cycloaddition of Enynes and Arynes
  作者：Mark Lautens、David Candito

  DOI：10.1055/s-0030-1261171

  日期：2011.9

  Examples of stereoselective reactions of aryne intermediates are rare in the literature. A stereoselective nickel-catalyzed [2+2+2] cycloaddition of 1,6-enynes with aryne intermediates is reported. Excellent stereoselectivities were observed when a substituent is adjacent to the olefin moiety resulting in trans- stereochemistry in the products. This reaction is capable of generating much complexity

  芳炔中间体的立体选择性反应的例子在文献中很少见。报道了立体选择性镍催化的 1,6-烯炔与芳炔中间体的 [2+2+2] 环加成反应。当取代基与烯烃部分相邻时，观察到优异的立体选择性，导致产物发生反式立体化学。该反应能够从简单且容易获得的起始材料中产生很多复杂性。此外，这些产品具有合成手柄，可以为进一步修改做好准备。
• Rhodium-Catalyzed Intramolecular Pauson-Khand Reaction
  作者：Yuji Koga、Toshitake Kobayashi、Koichi Narasaka

  DOI：10.1246/cl.1998.249

  日期：1998.3

  A rhodium dinuclear carbonyl complex, [RhCl(CO)2]2, serves as a catalyst of the intramolecular Pauson-Khand reaction. 1,6-Enynes are converted to cyclopentenone derivatives in high yield by heating in the presence of the catalyst under an atmospheric pressure of CO.

  铑双核羰基络合物 [RhCl(CO)2]2 可作为分子内 Pauson-Khand 反应的催化剂。1,6-烯炔通过在催化剂的存在下在大气压的 CO 下加热以高产率转化为环戊烯酮衍生物。
• Ru₃(CO)₁₂-Catalyzed Cyclocarbonylation of 1,6-Enynes to Bicyclo[3.3.0]octenones
  作者：Tsumoru Morimoto、Naoto Chatani、Yoshiya Fukumoto、Shinji Murai

  DOI：10.1021/jo970231x

  日期：1997.5.1
• First Ruthenium-Catalyzed Intramolecular Pauson−Khand Reaction
  作者：Teruyuki Kondo、Nobuyoshi Suzuki、Takumi Okada、Take-aki Mitsudo

  DOI：10.1021/ja970793y

  日期：1997.7.1