(R,R)-1,13-difluoro-5a,6,7,8,8a,9-hexahydro-5H-chromeno[3,2-d]xanthene

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: (R,R)-1,13-difluoro-5a,6,7,8,8a,9-hexahydro-5H-chromeno[3,2-d]xanthene
• 英文别名: (10R,14R)-4,20-difluoro-2,22-dioxapentacyclo[12.8.0.01,10.03,8.016,21]docosa-3(8),4,6,16(21),17,19-hexaene
• 化学式: C₂₀H₁₈F₂O₂
• 分子量: 328.359
• InChiKey: XNOXLRJOCBHSAR-YNCRUDOASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R,R)-1,13-difluoro-5a,6,7,8,8a,9-hexahydro-5H-chromeno[3,2-d]xanthene 、 二对甲苯膦 在 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 以92%的产率得到(5aR,8aR)-1,13-dis(di-p-tolylphosphanyl)-5a,6,7,8,8a,9-hexahydro-5H-chromeno[3,2-d]xanthene
  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：

  3-氟-2-羟基苯甲醛 在 C₃₉H₄₂IrNOP⁽¹⁺⁾*C₃₂H₁₂BF₂₄⁽¹⁺⁾ 、 氢气 、 potassium carbonate 、 sodium hydroxide 作用下， 以 乙醇 、 二氯甲烷 、 水 、 丙酮 为溶剂， 20.0 ℃ 、5.07 MPa 条件下， 反应 50.0h， 生成 (R,R)-1,13-difluoro-5a,6,7,8,8a,9-hexahydro-5H-chromeno[3,2-d]xanthene
  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

• 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：EP2876108B1

  公开（公告）日：2020-09-30
• 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