dimethyl 2,2-bis(3-(thiophen-2-yl)prop-2-yn-1-yl) propanedioate | 1372138-94-7

• 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: dimethyl 2,2-bis(3-(thiophen-2-yl)prop-2-yn-1-yl) propanedioate
• CAS: 1372138-94-7
• 化学式: C₁₉H₁₆O₄S₂
• 分子量: 372.466
• InChiKey: OEXWWUMNNSDNTL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.33
• 重原子数：
  25.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  dimethyl 2,2-bis(3-(thiophen-2-yl)prop-2-yn-1-yl) propanedioate 在 cyclopentadienylruthenium(II) trisacetonitrile hexafluorophosphate 、 二甲基亚砜 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以90%的产率得到C₁₉H₁₆O₅S₂
  参考文献：
  名称：

  Ruthenium-Catalyzed Transfer Oxygenative Cyclization of α,ω-Diynes: Unprecedented [2 + 2 + 1] Route to Bicyclic Furans via Ruthenacyclopentatriene

  摘要：

  A novel oxygen-atom-transfer process enables the catalytic [2 + 2 + 1] synthesis of bicyclic furans from alpha,omega-diynes with DMSO. [CpRu(AN)(3)]PF6 catalyzed the transfer oxygenative cyclization of diynes with aryl terminal groups, while those of diynes with alkyl terminal groups were effectively promoted by the corresponding Cp* complex. A mechanism for bicyclic furan formation via a ruthenacyclopentatriene was proposed on the basis of both experimental and theoretical studies.

  DOI：

  10.1021/ja302868s
• 作为产物：
  描述：

  3-thienylprop-2-ynyl methanesulfonate 、 丙二酸二甲酯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 9.5h， 以50%的产率得到dimethyl 2,2-bis(3-(thiophen-2-yl)prop-2-yn-1-yl) propanedioate
  参考文献：
  名称：

  Ruthenium-Catalyzed Transfer Oxygenative Cyclization of α,ω-Diynes: Unprecedented [2 + 2 + 1] Route to Bicyclic Furans via Ruthenacyclopentatriene

  摘要：

  A novel oxygen-atom-transfer process enables the catalytic [2 + 2 + 1] synthesis of bicyclic furans from alpha,omega-diynes with DMSO. [CpRu(AN)(3)]PF6 catalyzed the transfer oxygenative cyclization of diynes with aryl terminal groups, while those of diynes with alkyl terminal groups were effectively promoted by the corresponding Cp* complex. A mechanism for bicyclic furan formation via a ruthenacyclopentatriene was proposed on the basis of both experimental and theoretical studies.

  DOI：

  10.1021/ja302868s

文献信息

• Palladium(0)-Catalyzed Intermolecular Carbocyclization of (1,<i>n</i>)-Diynes and Bromophenols: An Efficient Route to Tricyclic Scaffolds
  作者：Lu Bai、Yini Yuan、Jingjing Liu、Jiaoyu Wu、Lingbo Han、Hui Wang、Yaoyu Wang、Xinjun Luan

  DOI：10.1002/anie.201601570

  日期：2016.6.6

  A novel palladium(0)‐catalyzed dearomative cyclization reaction of bromophenols with (1,n)‐diynes has been developed for building two new types of tricyclic architectures containing a quaternary carbon center. This method employs inexpensive bromophenols, and easily accessible tethered diynes. It exhibits a broad substrate scope and tolerates various functional groups. Preliminary results with commercially

  已开发出一种新颖的钯（0）催化的溴酚与（1，n）-二炔的脱芳香环化反应，用于构建两种新型的含季碳中心的三环结构。该方法使用廉价的溴酚和易于获得的束缚二炔。它具有广泛的底物范围，并能耐受各种官能团。商业上可获得的手性配体的初步结果表明，对映选择性变体对于两种环化过程都是可行的。
• Iridium-catalyzed [2+2+2] cycloaddition of α,ω-diynes with alkynyl ketones and alkynyl esters
  作者：Toru Hashimoto、Arisa Okabe、Takeshi Mizuno、Mao Izawa、Ryo Takeuchi

  DOI：10.1016/j.tet.2014.09.038

  日期：2014.11

  We found that the combination of [Ir(cod)Cl]2 and rac-BINAP served as an efficient catalyst for the [2+2+2] cycloaddition of 2,7-nonadiyne derivatives and related compounds with alkynyl ketones and alkynyl esters. The corresponding products were obtained in high yields under mild reaction conditions.

  我们发现[Ir（cod）Cl] 2和rac -BINAP的组合可作为有效的催化剂，用于2,7-壬二炔衍生物和相关化合物与炔基酮和炔基酯的[2 + 2 + 2]环加成。在温和的反应条件下，以高收率获得了相应的产物。
• Ruthenium-catalyzed hydrophosphinylative cyclization of 1,6-diynes. Stereoselective synthesis of exocyclic 1,3-dienylphosphine oxides
  作者：Yoshihiko Yamamoto、Kosuke Fukatsu、Hisao Nishiyama

  DOI：10.1039/c2cc34044e

  日期：——

  The first catalytic synthesis of exocyclic 1,3-dienylphosphine oxides was achieved by the ruthenium-catalyzed selective hydrophosphinylative cyclization of 1,6-diynes. A plausible mechanism involving a ruthenacyclopentatriene intermediate is proposed on the basis of the DFT calculations of model ruthenium complexes.

  在钌催化下，1,6-二炔发生了选择性氢化膦环化反应，首次催化合成了外环 1,3-二炔基膦氧化物。在对模型钌配合物进行 DFT 计算的基础上，提出了涉及钌环戊二烯中间体的合理机制。
• Ruthenium-Catalyzed Transfer-Hydrogenative Cyclization of 1,6-Diynes with Hantzsch 1,4-Dihydropyridine as a H₂Surrogate
  作者：Yoshihiko Yamamoto、Shota Mori、Masatoshi Shibuya

  DOI：10.1002/chem.201301846

  日期：2013.9.2

  AbstractThe transfer‐hydrogenative cyclization of 1,6‐diynes with Hantzsch 1,4‐dihydropyridine as a H2 surrogate was performed in the presence of a cationic ruthenium catalyst of the type [Cp′Ru(MeCN)3PF6]. Exocyclic 1,3‐dienes or their 1,4‐hydrogenation products, cycloalkenes, were selectively obtained, depending on the substrate structure and the reaction conditions.