[1-phenyl-3-(4'-methoxyphenyl)-2-propyn-1-ol]dicobalthexacarbonyl | 943866-37-3

• 英文名称: [1-phenyl-3-(4'-methoxyphenyl)-2-propyn-1-ol]dicobalthexacarbonyl
• CAS: 943866-37-3
• 化学式: C₂₂H₁₄Co₂O₈
• 分子量: 524.335
• InChiKey: FOKSIGXWFDSLSF-GVORHBCJSA-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-phenyl-3-(4'-methoxyphenyl)-2-propyn-1-ol]dicobalthexacarbonyl 、 tetrafluoroboric acid dimethyl ether complex 在 zinc 作用下， 以 二氯甲烷 为溶剂， 生成 d,l-[1,6-di(4'-methoxyphenyl)-3,4-diphenyl-1,5-hexadiyne]bis(dicobalthexacarbonyl) 、 meso-[1,6-di(4'-methoxyphenyl)-3,4-diphenyl-1,5-hexadiyne]bis(dicobalthexacarbonyl)
  参考文献：
  名称：

  Cross-Coupling of Cobalt-Complexed Propargyl Radicals:  Metal Core- and α- and γ-Aryl-Induced Chemo- and Diastereoselectivity

  摘要：

  Chemo- and diastereoselectivities of homo- and cross-coupling reactions of Co-2(CO)(6)-complexed propargyl radicals were studied. The alternative radical generation methodsreduction of respective cations with Zn or Cp2Co and one-step mediation with THF or Tf(2)Owere employed. In the case of cobalt complexes with terminal triple bonds, the product distribution is nearly statistical and dependent upon the reducing agent with the concentration of the cross-coupling product 8 falling in the range 38-49%. The diastereoselectivity varied widely (de 40-92%) with the preponderant formation of d,l-diastereoisomers 7-9 in both homo- and cross-coupling reactions. The highest level of stereocontrol was achieved in THF- and Tf2O-mediated reactions (de up to 92%), while the reductions with Cp2Co were inferior in both homo- and cross-coupling processes (de 40-56%). An introduction of a gamma-aromatic ring revealed a kinetic differentiation at the radical generation step that, in turn, resulted in a nonstatistical distribution of homo- and cross-dimers. The d,l-diastereoselectivity is found to be systematically lower for homo-dimer 16, containing a gamma-phenyl substituent at the triple bond (de: 16 14-64%; 7 52-84%). The observed chemoselectivities are accounted for on the basis of the computed values of charge distribution in the requisite cations.

  DOI：

  10.1021/om070180m
• 作为产物：
  描述：

  dicobalt octacarbonyl 、 苯甲醛 、 4-乙炔基苯甲醚 在 BuLi 作用下， 以 四氢呋喃 为溶剂， 以86.5%的产率得到[1-phenyl-3-(4'-methoxyphenyl)-2-propyn-1-ol]dicobalthexacarbonyl
  参考文献：
  名称：

  Cross-Coupling of Cobalt-Complexed Propargyl Radicals:  Metal Core- and α- and γ-Aryl-Induced Chemo- and Diastereoselectivity

  摘要：

  Chemo- and diastereoselectivities of homo- and cross-coupling reactions of Co-2(CO)(6)-complexed propargyl radicals were studied. The alternative radical generation methodsreduction of respective cations with Zn or Cp2Co and one-step mediation with THF or Tf(2)Owere employed. In the case of cobalt complexes with terminal triple bonds, the product distribution is nearly statistical and dependent upon the reducing agent with the concentration of the cross-coupling product 8 falling in the range 38-49%. The diastereoselectivity varied widely (de 40-92%) with the preponderant formation of d,l-diastereoisomers 7-9 in both homo- and cross-coupling reactions. The highest level of stereocontrol was achieved in THF- and Tf2O-mediated reactions (de up to 92%), while the reductions with Cp2Co were inferior in both homo- and cross-coupling processes (de 40-56%). An introduction of a gamma-aromatic ring revealed a kinetic differentiation at the radical generation step that, in turn, resulted in a nonstatistical distribution of homo- and cross-dimers. The d,l-diastereoselectivity is found to be systematically lower for homo-dimer 16, containing a gamma-phenyl substituent at the triple bond (de: 16 14-64%; 7 52-84%). The observed chemoselectivities are accounted for on the basis of the computed values of charge distribution in the requisite cations.

  DOI：

  10.1021/om070180m