4,4'-Dibromo-3,3'-dithienyldimethylsilane | 193140-52-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 4,4'-Dibromo-3,3'-dithienyldimethylsilane
• 英文别名: bis(4-bromo-3-thienyl)dimethylsilane；Bis(4-bromothiophen-3-yl)-dimethylsilane
• CAS: 193140-52-2
• 化学式: C₁₀H₁₀Br₂S₂Si
• 分子量: 382.215
• InChiKey: DDDZMOJMFNIARJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.16
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  56.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,4'-Dibromo-3,3'-dithienyldimethylsilane 在 正丁基锂 、 氧气 作用下， 以 四氢呋喃 为溶剂， 以42%的产率得到7,7,18,18-Tetramethyl-4,10,15,21-tetrathia-7,18-disilapentacyclo[17.3.0.02,6.08,12.013,17]docosa-1(22),2,5,8,11,13,16,19-octaene
  参考文献：
  名称：

  氰基-吉尔曼铜酸盐的选择性：10元环环烷的合成

  摘要：

  氰基-吉尔曼铜酸盐（衍生自二溴二噻吩基硫化物、二溴二噻吩基二甲基硅烷和二溴二噻吩基甲烷）与分子氧的氧化选择性地提供了 10 元环环烷，环烷 9 的 X 射线分析表明它具有反构象。

  DOI：

  10.1039/b008102g
• 作为产物：
  描述：

  3,4-二溴噻吩 、 二氯二甲基硅烷 在 正丁基锂 作用下， 以60%的产率得到4,4'-Dibromo-3,3'-dithienyldimethylsilane
  参考文献：
  名称：

  钯催化环合反应合成二噻吩并噻吩，环戊二噻吩和硅杂环戊二噻吩

  摘要：

  在四（三苯基膦）钯（0）​​存在下，溴化噻吩衍生物与六甲基二锡的分子内环化反应以中等至良好的产率得到了二噻吩并噻吩，环戊二噻吩和硅环戊二噻吩。

  DOI：

  10.1016/s0040-4039(97)00979-9

文献信息

• Novel electron-transfer oxidation of Lipshutz cuprates with 1,4-benzoquinones: an efficient homo-coupling reaction of aryl halides and its application to the construction of macrocyclic systems
  作者：Yoshihiro Miyake、Mo Wu、M. Jalilur Rahman、Masahiko Iyoda

  DOI：10.1039/b413842b

  日期：——

  The electron transfer reaction from Lipshutz cuprates, which can be easily prepared from aryl bromides, to 1,4-benzoquinones was found to proceed smoothly, affording either the corresponding homo-coupling products, in modest to excellent yields, or macrocyclic products selectively.

  从芳基溴化物容易制备的Lipshutz铜试剂到1,4-苯醌的电子转移反应进行顺利，可以适度到高产率地得到相应的偶联产物，或选择性地获得大环产物。
• Kabir, S. M. Humayun; Miura, Mami; Sasaki, Shigeru, Heterocycles, 2000, vol. 52, # 2, p. 761 - 774
  作者：Kabir, S. M. Humayun、Miura, Mami、Sasaki, Shigeru、Harada, Genta、Kuwatani, Yoshiyuki、Yoshida, Masato、Iyoda, Masahiko

  DOI：——

  日期：——
• Efficient Construction of Biaryls and Macrocyclic Cyclophanes via Electron-Transfer Oxidation of Lipshutz Cuprates
  作者：Yoshihiro Miyake、Mo Wu、M. Jalilur Rahman、Yoshiyuki Kuwatani、Masahiko Iyoda

  DOI：10.1021/jo0608063

  日期：2006.8.1

  An efficient method for the homocoupling of aryl halides by electron-transfer oxidation of Lipshutz cuprates (Ar2Cu(CN)Li-2) with organic electron acceptors is disclosed. Thus, various types of Lipshutz cuprates are prepared by successive treatment of aryl or heteroaryl bromides with tert-butyllithium and CuCN. The electron-transfer oxidation of Lipshutz cuprates with p-benzoquinones proceeds smoothly to afford the corresponding homocoupling products in moderate to good yields. Furthermore, it can be applied to the construction of either thiophene- or benzene-fused 10-membered ring cyclophanes. For the synthesis of 10-membered cyclophanes, the linear C-Cu-C structure of Lipshutz cuprates should be maintained in the dimetallacyclic intermediates, producing the large ring cyclophanes efficiently. The X-ray analysis of the cyclophanes reveals that the difference in the bridging atoms results in the different conformations of the macrocyclic rings. Thus, the silicon-bridged cyclophane 5a adopts a D-2-symmetric structure with a twisted rhombic arrangement of four thiophene rings, whereas the methylene- and oxygen-bridged cyclophanes 5b and 5c possess C2h- and C-2-symmetric structures with chair- and boatlike conformations, respectively. The H-1 NMR spectrum of C-2-symmetric 5c is temperature- dependent, and the activation energy (Delta G double dagger) for the conformational change is 10.1 kcal/mol.
• Selectivity of cyano-Gilman cuprates: synthesis of 10-membered ring cyclophanes
  作者：S. M. Humayun Kabir、Masahiko Iyoda

  DOI：10.1039/b008102g

  日期：——

  The oxidation of cyano-Gilman cuprates, derived from dibromodithienyl sulfide, dibromodithienyldimethylsilane and dibromodithienylmethane, with molecular oxygen furnishes 10-membered ring cyclophanes selectively and an X-ray analysis of cyclophane 9 reveals that it possesses an anti conformation.

  氰基-吉尔曼铜酸盐（衍生自二溴二噻吩基硫化物、二溴二噻吩基二甲基硅烷和二溴二噻吩基甲烷）与分子氧的氧化选择性地提供了 10 元环环烷，环烷 9 的 X 射线分析表明它具有反构象。
• Synthesis of dithienothiophenes, cyclopentadithiophene and silacyclopentadithiophenes using palladium-catalyzed cyclization
  作者：Masahiko Iyoda、Mami Miura、Shigeru Sasaki、S.M.Humayun Kabir、Yoshiyuki Kuwatani、Masato Yoshida

  DOI：10.1016/s0040-4039(97)00979-9

  日期：1997.6

  The intramolecular cyclization of bromothiophene derivatives with hexamethylditin in the presence of tetrakis(triphenylphosphine)palladium(0) gave dithienothiophenes, cyclopentadithiophene, and silacyclopentadithiophenes in moderate to good yields.

  在四（三苯基膦）钯（0）​​存在下，溴化噻吩衍生物与六甲基二锡的分子内环化反应以中等至良好的产率得到了二噻吩并噻吩，环戊二噻吩和硅环戊二噻吩。