(5aR,8aR)-1,13-dis(di-p-tolylphosphanyl)-5a,6,7,8,8a,9-hexahydro-5H-chromeno[3,2-d]xanthene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (5aR,8aR)-1,13-dis(di-p-tolylphosphanyl)-5a,6,7,8,8a,9-hexahydro-5H-chromeno[3,2-d]xanthene
• 英文别名: (+)-1,13-Bis[di(4-methylphenyl)phosphino]-(5aR,8aR,14aR)-5a,6,7,8,8a,9-hexahydro-5H-[1]benzopyrano[3,2-d]xanthene；[(10R,14R)-20-bis(4-methylphenyl)phosphanyl-2,22-dioxapentacyclo[12.8.0.01,10.03,8.016,21]docosa-3(8),4,6,16(21),17,19-hexaen-4-yl]-bis(4-methylphenyl)phosphane
• 化学式: C₄₈H₄₆O₂P₂
• 分子量: 716.84
• InChiKey: QGOSBHUTQQGVPA-OFSSCWCDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12
• 重原子数：
  52
• 可旋转键数：
  6
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  α,α'-bis(2-hydroxy-3-bromophenylidene)ketone 在 正丁基锂 、 C₃₉H₄₂IrNOP⁽²⁺⁾*C₃₂H₁₂BF₂₄^(1-) 、 氢气 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， -78.0~20.0 ℃ 、5.07 MPa 条件下， 反应 10.0h， 生成 (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：

  芳香族螺双膦配体：外消旋森田-贝利斯-希尔曼加合物的钯催化不对称烯丙基胺

  摘要：

  显示主链：双（膦）配体1的螺骨架主链在外消旋的Morita-Baylis-Hillman加合物与芳族胺的钯催化的不对称烯丙基胺化反应中产生了良好的区域和对映选择性。该方法为光学活性β-内酰胺衍生物（包括胆固醇药物依泽替米贝）的前体提供了便捷，高效的合成方法。

  DOI：

  10.1002/anie.201204925
• 作为试剂：
  描述：

  苯甲醛 在 三乙烯二胺 、 bis(η3-allyl-μ-chloropalladium(II)) 、 (5aR,8aR)-1,13-dis(di-p-tolylphosphanyl)-5a,6,7,8,8a,9-hexahydro-5H-chromeno[3,2-d]xanthene 、 potassium carbonate 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 生成 (S)-ethyl 2-(phenyl(phenylamino)methyl)acrylate
  参考文献：
  名称：

  芳香族螺双膦配体：外消旋森田-贝利斯-希尔曼加合物的钯催化不对称烯丙基胺

  摘要：

  显示主链：双（膦）配体1的螺骨架主链在外消旋的Morita-Baylis-Hillman加合物与芳族胺的钯催化的不对称烯丙基胺化反应中产生了良好的区域和对映选择性。该方法为光学活性β-内酰胺衍生物（包括胆固醇药物依泽替米贝）的前体提供了便捷，高效的合成方法。

  DOI：

  10.1002/anie.201204925

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：EP2876108A1

  公开（公告）日：2015-05-27

  Disclosed are aromatic spiroketal diphosphine ligands, preparation methods and uses thereof. The ligands have the structure of formula (I), in which R1, R2, R3, R4, R5, R6, R7, R8, 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.

  本发明公开了芳香族螺酮二膦配体及其制备方法和用途。这些配体具有式（I）结构，其中 R1、R2、R3、R4、R5、R6、R7、R8、X 和 n 的定义如说明书所述。芳香族螺酮二膦配体由芳香族螺酮化合物制备。还公开了芳香族螺酮化合物的制备方法。制备方法简单，可制备外消旋或手性芳族螺酮二膦配体。这些配体可用作不对称催化反应的催化剂，具有经济实用性和工业应用前景。
• 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
• PROCESS FOR SYNTHESIS OF EZETIMIBE AND INTERMEDIATES USED IN SAID PROCESS
  申请人：Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences

  公开号：EP2876102B1

  公开（公告）日：2016-12-07
• US9527862B2
  申请人：——

  公开号：US9527862B2

  公开（公告）日：2016-12-27
• Aromatic Spiroketal Bisphosphine Ligands: Palladium-Catalyzed Asymmetric Allylic Amination of Racemic Morita-Baylis-Hillman Adducts
  作者：Xiaoming Wang、Fanye Meng、Yan Wang、Zhaobin Han、Yong-Jun Chen、Li Liu、Zheng Wang、Kuiling Ding

  DOI：10.1002/anie.201204925

  日期：2012.9.10

  and enantioselectivity in the palladium‐catalyzed asymmetric allylic amination of racemic Morita–Baylis–Hillman adducts with aromatic amines. The methodology provides a facile and efficient synthesis of precursors for optically active β‐lactam derivatives, including the cholesterol drug Ezetimibe.

  显示主链：双（膦）配体1的螺骨架主链在外消旋的Morita-Baylis-Hillman加合物与芳族胺的钯催化的不对称烯丙基胺化反应中产生了良好的区域和对映选择性。该方法为光学活性β-内酰胺衍生物（包括胆固醇药物依泽替米贝）的前体提供了便捷，高效的合成方法。