(2S,4S)-4-dicyclohexylphosphino-2-diphenylphosphinomethylpyrrolidine | 112522-02-8

• 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: (2S,4S)-4-dicyclohexylphosphino-2-diphenylphosphinomethylpyrrolidine
• 英文别名: dicyclohexyl-[(3S,5S)-5-(diphenylphosphanylmethyl)pyrrolidin-3-yl]phosphane
• CAS: 112522-02-8
• 化学式: C₂₉H₄₁NP₂
• 分子量: 465.599
• InChiKey: IGMXXCSYLIDCLZ-OUTSHDOLSA-N

物化性质

• 沸点：
  580.5±43.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  二碳酸二叔丁酯 、 (2S,4S)-4-dicyclohexylphosphino-2-diphenylphosphinomethylpyrrolidine 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 (2S,4S)-N-(t-butoxycarbonyl)-4-(dicyclohexylphosphino)-2-[(diphenylphosphino)methyl]pyrrolidine
  参考文献：
  名称：

  Asymmetric Reactions Catalyzed by Chiral Metal Complex. LIX. Preparations of Chiral Pyrrolidinebisphosphines Bearing Two Different Types of Phosphino Groups and Their Use in Efficient Catalytic Asymmetric Hydrogenation.

  摘要：

  手性吡咯烷双磷配体（2S-cis）-BCPM 和（2S-cis）-BCPP，分别具有两种不同类型的磷基团：双环己基磷基团和二苯基磷基团，基于我们开发高效配体的设计理念进行了设计和制备。通过使用BCPM、BCPP、BPPM和BCCP的中性铑(I)配合物，在酮氨基酸内酯的非对称加氢反应中实验验证了该设计理念的有效性。研究发现（2S-cis）-BCPM的铑(I)配合物是最有效的催化剂（底物/催化剂 >约104，>90%酯选窗率 (R)）。

  DOI：

  10.1248/cpb.42.481
• 作为产物：
  描述：

  (2S-cis)-4-(dicyclohexylphosphinyl)-2-<(diphenylphosphinyl)-methyl>pyrrolidine 在 三氯硅烷 、 三乙胺 作用下， 以 乙腈 为溶剂， 反应 3.0h， 生成 (2S,4S)-4-dicyclohexylphosphino-2-diphenylphosphinomethylpyrrolidine
  参考文献：
  名称：

  Asymmetric Reactions Catalyzed by Chiral Metal Complex. LIX. Preparations of Chiral Pyrrolidinebisphosphines Bearing Two Different Types of Phosphino Groups and Their Use in Efficient Catalytic Asymmetric Hydrogenation.

  摘要：

  手性吡咯烷双磷配体（2S-cis）-BCPM 和（2S-cis）-BCPP，分别具有两种不同类型的磷基团：双环己基磷基团和二苯基磷基团，基于我们开发高效配体的设计理念进行了设计和制备。通过使用BCPM、BCPP、BPPM和BCCP的中性铑(I)配合物，在酮氨基酸内酯的非对称加氢反应中实验验证了该设计理念的有效性。研究发现（2S-cis）-BCPM的铑(I)配合物是最有效的催化剂（底物/催化剂 >约104，>90%酯选窗率 (R)）。

  DOI：

  10.1248/cpb.42.481

文献信息

• Asymmetric Reactions Catalyzed by Chiral Metal Complex. LIX. Preparations of Chiral Pyrrolidinebisphosphines Bearing Two Different Types of Phosphino Groups and Their Use in Efficient Catalytic Asymmetric Hydrogenation.
  作者：Toshiaki MORIMOTO、Hisashi TAKAHASHI、Kazuo ACHIWA

  DOI：10.1248/cpb.42.481

  日期：——

  Chiral pyrrolidinebisphosphine ligands, (2S-cis)-BCPM and (2S-cis)-BCPP, bearing two different types of phosphino groups, a dicyclohexylphosphino group and a diphenylphosphino groups, were designed and prepared on the basis of our design concept for developing highly efficient ligands. The validity of the concept was confirmed experimentally in the asymmetric hydrogenation of ketopantolactone using neutral rhodium(I) complexes of BCPM, BCPP, BPPM, and BCCP. The rhodium(I) complex of (2S-cis)-BCPM was found to be the most effective catalyst (substrate/catalyst >ca. 104, >90%ee (R)).

  手性吡咯烷双磷配体（2S-cis）-BCPM 和（2S-cis）-BCPP，分别具有两种不同类型的磷基团：双环己基磷基团和二苯基磷基团，基于我们开发高效配体的设计理念进行了设计和制备。通过使用BCPM、BCPP、BPPM和BCCP的中性铑(I)配合物，在酮氨基酸内酯的非对称加氢反应中实验验证了该设计理念的有效性。研究发现（2S-cis）-BCPM的铑(I)配合物是最有效的催化剂（底物/催化剂 >约104，>90%酯选窗率 (R)）。
• Chiral phosphinopyrrolidine compounds and their use for asymmetric
  申请人：——

  公开号：US04879389A1

  公开（公告）日：1989-11-07

  New chiral phosphinopyrrolidine compounds of the general formula: ##STR1## wherein R.sup.1 is a hydrogen atom, --COR, --COOR, --CONHR or --SO.sub.2 --R where R is an alkyl or aryl group, R.sup.2 and R.sup.3 each represents independently an aryl group which may have a substituent or substituents, and R.sup.4 and R.sup.5 each represents independently an aliphatic or cycloaliphatic hydrocarbyl group which may have a substituent or substituents, as well as the use of these compounds as ligand for a metal complex catalyst for asymmetric synthesis of optically active compounds. The new chiral phosphinopyrrolidine compounds are useful ligands which attain both of high optical yield and high reaction efficiency in catalytic asymmetric reduction.

  新手性磷酰吡咯烷化合物的一般式为：##STR1## 其中R.sup.1是氢原子，-COR，-COOR，-CONHR或-SO.sub.2-R，其中R是烷基或芳基基团，R.sup.2和R.sup.3各自独立地表示可能具有取代基的芳基基团，R.sup.4和R.sup.5各自独立地表示可能具有取代基的脂肪或环脂烃基团，以及这些化合物作为金属配合物催化剂的配体用于不对称合成光学活性化合物。这些新的手性磷酰吡咯烷化合物是有用的配体，可在催化不对称还原中实现高光学产率和高反应效率。
• Phosphinopyrroline compounds and process for producing the same
  申请人：Fuji Yakuhin Kogyo Kabushiki Kaisha

  公开号：US06229019B1

  公开（公告）日：2001-05-08

  A process for producing phosphinopyrrolidine compounds especially useful for preparing optically active compounds through asymmetric synthesis which is a simplified short process requiring neither a step necessitating a high-temperature and high-pressure reaction nor special equipment for production. A phosphino group is incorporated into a pyrrolidine compound in the presence of a boron compound, and the resultant pyrrolidine compound is further reacted while protecting the phosphorous atom, whereby a dicyclohexylphosphino group can be efficiently incorporated into the pyrrolidine nucleus in the 4-position. Thus, the target phosphinopyrrolidine compounds useful as ligands for asymmetric synthesis catalysts can be obtained through a significantly small number of steps without resort to troublesome steps such as the step of reducing a phenyl group at high temperature and high pressure.

  一种生产膦吡咯烷化合物的方法，尤其适用于通过不对称合成制备光学活性化合物，该方法是一种简化的短步骤过程，不需要高温高压反应步骤或特殊的生产设备。在硼化合物的存在下将膦基团合并到吡咯烷化合物中，然后在保护磷原子的情况下进一步反应所得的吡咯烷化合物，从而可以在4位点上高效地将二环己基膦基团合并到吡咯烷核中。因此，可以通过显著少量的步骤获得目标膦吡咯烷化合物，这些化合物可用作不对称合成催化剂的配体，无需采用高温高压还原苯基团等麻烦步骤。
• New chiral phosphinopyrrolidine compounds and their use for asymetric synthesis of optically active compounds
  申请人：Achiwa, Kazuo

  公开号：EP0251164A2

  公开（公告）日：1988-01-07

  New chiral phosphinopyrrolidine compounds of the general formula: or wherein R1 is a hydrogen atom, -COR, -COOR, -CONHR or -SO2R where R is an alkyl or aryl group, R2 and R3 each represents independently an aryl group which may have a substituent or substituents, and RA and R5 each represents independently an aliphatic or cycloaliphatic hydrocarbyl group which may have a substituent or substituents, as well as the use of these compound as ligand for a metal complex catalyst for asymmetric synthesis or optically active compounds. The new chiral phosphinopyrrolidine compounds are useful ligands which attain both of high optical yield and high reaction efficiency in catalytic asymmetric reduction.

  通式如下的新型手性膦基吡咯烷化合物 或 其中 R1 是氢原子、-COR、-COOR、-CONHR 或 -SO2R 其中 R 是烷基或芳基，R2 和 R3 分别独立地代表芳基（可带有一个或多个取代基），RA 和 R5 分别独立地代表脂肪族或环脂族烃基（可带有一个或多个取代基）。新的手性膦基吡咯烷化合物是一种有用的配体，在催化不对称还原反应中可获得高光学产率和高反应效率。
• NOVEL PHOSPHINOPYRROLIDINE COMPOUNDS AND PROCESS FOR PRODUCING THE SAME
  申请人：Daiichi Fine Chemical Co., Ltd.

  公开号：EP0989135B1

  公开（公告）日：2003-03-05