(2E,6E)-2-(2-(benzyloxy)-3-fluorobenzylidene)-6-(2,3-bis(benzyloxy)benzylidene)cyclohexanone | 1569309-80-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: (2E,6E)-2-(2-(benzyloxy)-3-fluorobenzylidene)-6-(2,3-bis(benzyloxy)benzylidene)cyclohexanone
• CAS: 1569309-80-3
• 化学式: C₄₁H₃₅FO₄
• 分子量: 610.725
• InChiKey: QCENDPLTSNEUDT-BCEWYCLDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.78
• 重原子数：
  46.0
• 可旋转键数：
  11.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  44.76
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (2E,6E)-2-(2-(benzyloxy)-3-fluorobenzylidene)-6-(2,3-bis(benzyloxy)benzylidene)cyclohexanone 在 C₃₉H₄₂IrNOP⁽¹⁺⁾*C₃₂H₁₂BF₂₄⁽¹⁺⁾ 、 氢气 、 5%-palladium/activated carbon 作用下， 以 二氯甲烷 为溶剂， 20.0 ℃ 、2.03 MPa 条件下， 反应 30.0h， 以86%的产率得到(R,R,R)-13-fluoro-5a,6,7,8,8a,9-hexahydro-5H-chromeno[3,2-d]xanthen-1-ol
  参考文献：
  名称：

  实际的不对称催化合成螺缩酮和手性二膦配体

  摘要：

  AbstractA practical procedure has been developed for efficient synthesis of chiral aromatic spiroketals and the relevant diphosphine ligands. The procedure includes first asymmetric hydrogenation of readily available α,α′‐bis(2‐benzyloxyarylidene) ketones catalyzed by the Ir(I)/SpinPHOX (S,S)‐1a (0.5–1 mol%) and subsequent hydrogenative deprotection of the resultant benzyl ethers catalyzed by palladium on carbon (Pd/C), as well as simultaneous spiroketalization of the corresponding diphenolic ketones by (S,S)‐1a in one pot. The corresponding chiral aromatic spiroketals (R,R,R)‐4a–j have been obtained in high yields (77–94%) with good diastereoselectivities (trans/cis=81/19 to 96/4), and excellent enantioselectivities for the trans products (97–>99% ee). In addition, the reaction of aromatic spiroketal difluoride (R,R,R)‐4b with potassiodiarylphosphide (KPAr2) in refluxing tertahydrofuran (THF) has also provided an alternative and practical synthesis of chiral spiroketal‐based diphosphine (SKP) ligands in 78–95% yields on multigram scale.magnified image

  DOI：

  10.1002/adsc.201300380
• 作为产物：
  描述：

  溴甲苯 在 potassium carbonate 、 sodium hydroxide 作用下， 以 四氢呋喃 、 乙醇 、 水 、 丙酮 为溶剂， 反应 20.0h， 生成 (2E,6E)-2-(2-(benzyloxy)-3-fluorobenzylidene)-6-(2,3-bis(benzyloxy)benzylidene)cyclohexanone
  参考文献：
  名称：

  实际的不对称催化合成螺缩酮和手性二膦配体

  摘要：

  AbstractA practical procedure has been developed for efficient synthesis of chiral aromatic spiroketals and the relevant diphosphine ligands. The procedure includes first asymmetric hydrogenation of readily available α,α′‐bis(2‐benzyloxyarylidene) ketones catalyzed by the Ir(I)/SpinPHOX (S,S)‐1a (0.5–1 mol%) and subsequent hydrogenative deprotection of the resultant benzyl ethers catalyzed by palladium on carbon (Pd/C), as well as simultaneous spiroketalization of the corresponding diphenolic ketones by (S,S)‐1a in one pot. The corresponding chiral aromatic spiroketals (R,R,R)‐4a–j have been obtained in high yields (77–94%) with good diastereoselectivities (trans/cis=81/19 to 96/4), and excellent enantioselectivities for the trans products (97–>99% ee). In addition, the reaction of aromatic spiroketal difluoride (R,R,R)‐4b with potassiodiarylphosphide (KPAr2) in refluxing tertahydrofuran (THF) has also provided an alternative and practical synthesis of chiral spiroketal‐based diphosphine (SKP) ligands in 78–95% yields on multigram scale.magnified image

  DOI：

  10.1002/adsc.201300380