2,6-bis-(2-benzyloxy)-benzylidene-cyclohexanone | 110827-88-8

• 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: 2,6-bis-(2-benzyloxy)-benzylidene-cyclohexanone
• 英文别名: (2E,6E)-2,6-bis(2-(benzyloxy)benzylidene)cyclohexanone；2,6-Bis[2-(benzyloxy)benzylidene]cyclohexanone；(2E,6E)-2,6-bis[(2-phenylmethoxyphenyl)methylidene]cyclohexan-1-one
• CAS: 110827-88-8
• 化学式: C₃₄H₃₀O₃
• 分子量: 486.61
• InChiKey: QDLAGLJWDAKIHR-WECXDZCISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  37
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,6-bis-(2-benzyloxy)-benzylidene-cyclohexanone 在 C₃₉H₄₂IrNOP⁽¹⁺⁾*C₃₂H₁₂BF₂₄⁽¹⁺⁾ 、 氢气 作用下， 以 二氯甲烷 为溶剂， 20.0 ℃ 、5.07 MPa 条件下， 反应 6.0h， 以87%的产率得到(2R,6R)-2,6-bis(2-(benzyloxy)benzyl)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
• 作为产物：
  描述：

  水杨醛 在 potassium carbonate 、 sodium hydroxide 作用下， 以 乙醇 、 水 、 丙酮 为溶剂， 反应 20.0h， 生成 2,6-bis-(2-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

文献信息

• Synthesis of grisan
  作者：Sándor Antus、Eszter Baitz-Gács、Günther Snatzke、Judit Vas

  DOI：10.1016/s0040-4020(01)88168-0

  日期：1986.1
• COMPOUNDS OF CHIRAL AROMATIC SPIROKETAL DIPHOSPHINE LIGANDS, PREPARATION METHODS AND USES THEREOF
  申请人：SHANGHAI INSTITUTE OF ORGANIC CHEMISTRY, CHINESE ACADEMY OF SCIENCES

  公开号：US20150252055A1

  公开（公告）日：2015-09-10

  Disclosed are aromatic spiroketal diphosphine ligands, preparation methods and uses thereof. The ligands have the structure of formula (I), in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , X and n are defined as such described in the specification. The aromatic spiroketal diphosphine ligands are prepared from aromatic spiroketal compounds. Also disclosed are the preparation methods of aromatic spiroketal compounds. The preparation methods are simple and can produce racemic or chiral aromatic spiroketal diphosphine ligands. The ligands can be used as catalysts of asymmetrical catalytic reactions having economical practicability and industry application prospect.
• US9527862B2
  申请人：——

  公开号：US9527862B2

  公开（公告）日：2016-12-27
• Practical Asymmetric Catalytic Synthesis of Spiroketals and Chiral Diphosphine Ligands
  作者：Xubin Wang、Peihua Guo、Xiaoming Wang、Zheng Wang、Kuiling Ding

  DOI：10.1002/adsc.201300380

  日期：2013.10.11

  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