S-trans-2,3-di-3-chloropropyl-1,4-bis-(1,3-dioxo-4,4,5,5-tetramethyl-2-borolanyl)-1,3-butadiene | 178693-17-9

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: S-trans-2,3-di-3-chloropropyl-1,4-bis-(1,3-dioxo-4,4,5,5-tetramethyl-2-borolanyl)-1,3-butadiene
• 英文别名: 2-[(E,3E)-6-chloro-2-(3-chloropropyl)-3-[(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methylidene]hex-1-enyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 178693-17-9
• 化学式: C₂₂H₃₈B₂Cl₂O₄
• 分子量: 459.069
• InChiKey: XLHKVIGXZXWFTQ-YTEMWHBBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.14
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tricarbonylbis(cis-cyclooctene)iron 、 S-trans-2,3-di-3-chloropropyl-1,4-bis-(1,3-dioxo-4,4,5,5-tetramethyl-2-borolanyl)-1,3-butadiene 以 正己烷 为溶剂， 以30%的产率得到[2,3-di-3-chloropropyl-1,4-bis-(1,3-dioxo-4,4,5,5-tetramethyl-2-borolanyl)-1,3-butadiene]Fe(CO)3
  参考文献：
  名称：

  Iron complexes of dioxoborolanylbutadienes

  摘要：

  The first [2,3-dialkyl-1,4-bis(1,3-dioxo-4,4,5,5-tetramethyl-2-borolanyl]-1,3-butadiene]Fe(CO)(3) complexes (2, alkyl = n-butyl; 3, alkyl = cyclopentyl; 4, 'alkyl' = phenyl; 5, alkyl = 3-chloropropyl) have been prepared from the reaction of bis(cis-cyclooctadiene)Fe(CO)(3) (1) with the borolanylbutadienes. The X-ray crystal structures of 2 and 3 are reported. The geometries of the coordinated ligands are compared with those of the free ligands. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(99)00136-x
• 作为产物：
  描述：

  5-氯-1-戊炔硼酸频那醇酯 在 Cp₂ZrCl₂ 、 n-BuLi 、 HCl 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 为溶剂， 以15%的产率得到2-[(1E,3E)-7-chloro-2-(3-chloropropyl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hepta-1,3-dienyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  Zirconocene-Mediated Preparation of 1,3-, 1,4-, and 2,3-Dibora-1,3-butadienes:  Their Isolation and Characterization and Use in Suzuki−Miyaura Coupling

  摘要：

  Hydrozirconation of 1-alkynyl pinacolboronates, 1, with HZrCp(2)Cl provides gem-borazirconocenes 2. The latter when treated with CuBr gives the homocoupled (1E,3E)-2,3-dibora-1,3-butadienes, 3, in good yield (62-67%). The reaction works even for hindered 2 (R = t-Bu). Structure 3 was assigned on the basis of NMR. Suzuki-Miyaura coupling of 3a (R = n-Bu) with PhI in the presence of CsF leads to the replacement of both boron groups by phenyl and hydrogen to give 6 in 76% yield. Zirconocene-mediated coupling of 1 leads to diastereomeric products: (1E,3E)-1,3-dibora-1,3-butadienes, 4, in 7-26% isolated yields and (1E,3E)-1,4-dibora-1,3-butadienes, 5, in 17-34% isolated yields. The two isomers can be separated by selective precipitation of 5 from the reaction mixture in pentane (-20 degrees C) followed by silica gel chromatography to give pure 4. The reaction does not work when R in 1 is the t-Bu group. Assignments of structures for 4 and 5 were done on the basis of 1D and 2D NMR experiments. In addition, a single-crystal X-ray analysis of 5a showed it to be a highly planar and linearly oriented molecule. Suzuki-Miyaura coupling of 4a proceeded to replace the terminal boron group exclusively, while the internal boron group of 4a remained intact.

  DOI：

  10.1021/om960178n