5a,6,7,8,8a,9-hexahydro-5H-chromeno[3,2-d]xanthene | 6722-10-7

• 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: 5a,6,7,8,8a,9-hexahydro-5H-chromeno[3,2-d]xanthene
• 英文别名: 2,22-Dioxapentacyclo[12.8.0.01,10.03,8.016,21]docosa-3,5,7,16,18,20-hexaene；2,22-dioxapentacyclo[12.8.0.01,10.03,8.016,21]docosa-3,5,7,16,18,20-hexaene
• CAS: 6722-10-7
• 化学式: C₂₀H₂₀O₂
• 分子量: 292.378
• InChiKey: MITLHOUXQKXRCL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  22
• 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：
  2

反应信息

• 作为产物：
  描述：

  2-苄氧基苯甲醛 在 C₃₉H₄₂IrNOP⁽¹⁺⁾*C₃₂H₁₂BF₂₄⁽¹⁺⁾ 、 氢气 、 sodium hydroxide 作用下， 以 乙醇 、 二氯甲烷 、 水 为溶剂， 20.0 ℃ 、5.07 MPa 条件下， 反应 42.0h， 生成 (R,R)-5a,6,7,8,8a,9-hexahydro-5H-chromeno[3,2-d]xanthene 、 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

• Catalytic Asymmetric Synthesis of Aromatic Spiroketals by SpinPhox/Iridium(I)-Catalyzed Hydrogenation and Spiroketalization of α,α′-Bis(2-hydroxyarylidene) Ketones
  作者：Xiaoming Wang、Zhaobin Han、Zheng Wang、Kuiling Ding

  DOI：10.1002/anie.201106488

  日期：2012.1.23

  From spiro to spiro: An iridium(I) complex with a spiral P,N ligand (SpinPhox) is highly efficient in the catalytic asymmetric hydrogenation of α,α′‐bis(2‐hydroxyarylidene) ketones to afford the corresponding aromatic spiroketals in high yields with excellent diastereo‐ and enantioselectivities (see scheme). The complex plays a dual role in the reaction, acting as catalyst for both the hydrogenation

  从螺线到螺线：具有螺旋P，N配体（SpinPhox）的铱（I）络合物在α，α'-双（2-羟基亚芳基）酮的催化不对称加氢反应中提供高效率的相应芳族螺环化合物非常高效产生的非对映异构和对映异构选择性极佳（参见方案）。该络合物在反应中起双重作用，既充当CC键氢化和随后双酚酮的螺缩酮化的催化剂。
• 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