1-bromo-1'-(1-hydroxyisopropyl)ferrocene | 869893-79-8

• 英文名称: 1-bromo-1'-(1-hydroxyisopropyl)ferrocene
• CAS: 869893-79-8
• 化学式: C₁₃H₁₅BrFeO
• 分子量: 323.012
• InChiKey: BJHIFOYEVNICKA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  1-bromo-1'-(1-hydroxyisopropyl)ferrocene 、 lithium aluminium tetrahydride 在 aluminum chloride 作用下， 以 乙醚 为溶剂， 以68.5%的产率得到1-bromo-1'-isopropylferrocene
  参考文献：
  名称：

  Biferrocene−M(mnt)₂ Charge-Transfer Complexes (M = Ni, Co; mnt = Maleonitriledithiolate). Structure, Valence States, and Magnetic Properties

  摘要：

  Charge-transfer salts of branched-alkyl biferrocenes, (1', 1"'-R-2-1,1"-biferrocene)[Ni(mnt)(2)] (1a, R = isopropyl; 2a, R = dineopentyl) and (1', 1"'-R2-1,1"-biferrocene)(2)[Co(mnt)(2)](2) (1b, R = isopropyl; 2b, R = dineopentyl), were prepared. Their valence states were investigated using X-ray crystallography and Mossbauer spectroscopy. Complexes 1a and 1b show segregated-stack crystal structures that contain columns of acceptors, whereas structures of 2a and 2b, which contain bulky donors, are rather discrete. All of the complexes contain mixed-valent biferrocenium monocations. A two-step valence transition was found in complex 1a. The crystal contains two crystal log raphically independent cations: one undergoes valence localization below room temperature; the other undergoes valence localization below ca. 130 K. The former transition is derived from asymmetry of the crystal environment around the cation, whereas the latter one is caused by symmetry lowering coupled with a spin-Peierls transition (T-C = 133.2 K) associated with the dimerization of the acceptors. This compound was found to exhibit a dielectric response based on valence tautomerization. Other complexes (1b, 2a, and 2b) show a valence-trapped state. In all complexes, charge localization was found to occur through local electrostatic interactions between the donor's cationic moiety and the acceptor's electronegative moieties.

  DOI：

  10.1021/ic048285u
• 作为产物：
  描述：

  1,1'-dibromoferrocene 、 丙酮 在 n-butyllithium 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以38.8%的产率得到1-bromo-1'-(1-hydroxyisopropyl)ferrocene
  参考文献：
  名称：

  Biferrocene−M(mnt)₂ Charge-Transfer Complexes (M = Ni, Co; mnt = Maleonitriledithiolate). Structure, Valence States, and Magnetic Properties

  摘要：

  Charge-transfer salts of branched-alkyl biferrocenes, (1', 1"'-R-2-1,1"-biferrocene)[Ni(mnt)(2)] (1a, R = isopropyl; 2a, R = dineopentyl) and (1', 1"'-R2-1,1"-biferrocene)(2)[Co(mnt)(2)](2) (1b, R = isopropyl; 2b, R = dineopentyl), were prepared. Their valence states were investigated using X-ray crystallography and Mossbauer spectroscopy. Complexes 1a and 1b show segregated-stack crystal structures that contain columns of acceptors, whereas structures of 2a and 2b, which contain bulky donors, are rather discrete. All of the complexes contain mixed-valent biferrocenium monocations. A two-step valence transition was found in complex 1a. The crystal contains two crystal log raphically independent cations: one undergoes valence localization below room temperature; the other undergoes valence localization below ca. 130 K. The former transition is derived from asymmetry of the crystal environment around the cation, whereas the latter one is caused by symmetry lowering coupled with a spin-Peierls transition (T-C = 133.2 K) associated with the dimerization of the acceptors. This compound was found to exhibit a dielectric response based on valence tautomerization. Other complexes (1b, 2a, and 2b) show a valence-trapped state. In all complexes, charge localization was found to occur through local electrostatic interactions between the donor's cationic moiety and the acceptor's electronegative moieties.

  DOI：

  10.1021/ic048285u

文献信息

• Pd-Catalyzed Highly Enantioselective Synthesis of Planar Chiral Ferrocenylpyridine Derivatives
  作者：De-Wei Gao、Chao Zheng、Qing Gu、Shu-Li You

  DOI：10.1021/acs.organomet.5b00730

  日期：2015.9.28

  A highly efficient synthesis of planar chiral ferrocenylpyridine derivatives via Pd-catalyzed intramolecular C-H arylation was developed, and quantitative yields and excellent enantioselectivity were obtained for a wide range of substrates. Notably, the catalyst loading could be lowered to 0.2 mol %, which represents the highest catalytic efficiency found for asymmetric C-H bond activation (TON up to 495). These compounds could be easily transformed to pyridine N-oxides, displaying promising catalytic reactivity in the asymmetric opening of meso-epoxide. Moreover, computational investigations were conducted to clarify the origin of the excellent enantioselectivity. The compatibility of large-scale synthesis and low catalyst loading should enhance the practicality of the synthetic application of the current method.