(R)-6-bromo-2'-diphenylphosphino-1,1'-binaphthalen-2-ol | 213314-17-1

• 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: (R)-6-bromo-2'-diphenylphosphino-1,1'-binaphthalen-2-ol
• 英文别名: 2'-diphenylphosphino-2-hydroxy-6-bromo-1,1'-binaphthalene；2'-diphenylphosphino-2-hydroxy-6-bromo-1,1'-binaphthyl；6-bromo-1-(2-diphenylphosphanylnaphthalen-1-yl)naphthalen-2-ol
• CAS: 213314-17-1
• 化学式: C₃₂H₂₂BrOP
• 分子量: 533.404
• InChiKey: KSWCSQFBIJPBNB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  35
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-6-bromo-2'-diphenylphosphino-1,1'-binaphthalen-2-ol 在 potassium phosphate 、 四(三苯基膦)钯 、 三乙胺 作用下， 以 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 40.0h， 生成 (R)-2'-diphenylphosphino-6-vibyl-1,1'-binaphthalen-2-yl (S)-1,1'-binaphthalene-2,2'-diyl phosphite
  参考文献：
  名称：

  高度交联聚合物基质中烯烃的不对称加氢甲酰化

  摘要：

  当使用聚合物固定的手性膦-亚磷酸酯-Rh(I) 配合物时，苯乙烯的不对称加氢甲酰化得到 2- 和 3-苯基丙醛，底物/催化剂比为 2000，异/正比为 84/16 至 89/11和 89% R 对映体过量的 2-苯基丙醛；这些结果在催化活性、区域选择性和对映选择性方面处于最高水平。检查了催化剂的回收再利用。乙酸乙烯酯、(Z)-2-丁烯和3,3,3-三氟丙烯的不对称加氢甲酰化也用聚合物负载的催化剂成功进行。

  DOI：

  10.1246/bcsj.72.1911
• 作为产物：
  描述：

  (R)-6-bromo-2'-diphenylphosphinoyl-1,1'-binaphthalen-2-ol 在 三氯硅烷 、 三乙胺 作用下， 以 xylene 为溶剂， 反应 22.0h， 以65%的产率得到(R)-6-bromo-2'-diphenylphosphino-1,1'-binaphthalen-2-ol
  参考文献：
  名称：

  高度交联聚合物基质中烯烃的不对称加氢甲酰化

  摘要：

  当使用聚合物固定的手性膦-亚磷酸酯-Rh(I) 配合物时，苯乙烯的不对称加氢甲酰化得到 2- 和 3-苯基丙醛，底物/催化剂比为 2000，异/正比为 84/16 至 89/11和 89% R 对映体过量的 2-苯基丙醛；这些结果在催化活性、区域选择性和对映选择性方面处于最高水平。检查了催化剂的回收再利用。乙酸乙烯酯、(Z)-2-丁烯和3,3,3-三氟丙烯的不对称加氢甲酰化也用聚合物负载的催化剂成功进行。

  DOI：

  10.1246/bcsj.72.1911

文献信息

• Chiral Phosphine Lewis Bases Catalyzed Asymmetric aza-Baylis−Hillman Reaction of N-Sulfonated Imines with Activated Olefins
  作者：Min Shi、Lian-Hui Chen、Chao-Qun Li

  DOI：10.1021/ja0447255

  日期：2005.3.1

  In the aza-Baylis-Hillman reaction of N-sulfonated imines (N-arylmethylidene-4-methylbenzenesulfonamides and others) with methyl vinyl ketone, ethyl vinyl ketone, and acrolein, we found that, in the presence of a catalytic amount of chiral phosphine Lewis base such as (R)-2'-diphenylphosphanyl-[1,1']binaphthalenyl-2-ol LB1 (10 mol %) and molecular sieve 4A, the corresponding aza-Baylis-Hillman adducts

  在 N-磺化亚胺（N-芳基亚甲基-4-甲基苯磺酰胺等）与甲基乙烯基酮、乙基乙烯基酮和丙烯醛的 aza-Baylis-Hillman 反应中，我们发现，在催化量的手性膦存在下路易斯碱如 (R)-2'-二苯基膦酰基-[1,1']联萘-2-醇 LB1 (10 mol%) 和分子筛 4A，相应的 aza-Baylis-Hillman 加合物可以以良好的收率获得分别在低温（约 -30 至 -20 摄氏度）或室温下在 THF 中从良好到高 ee（70-95% ee）。在 CH2Cl2 中，在 40 摄氏度加热后，N-磺化亚胺与丙烯酸苯酯或萘基丙烯酸酯的 aza-Baylis-Hillman 反应以良好至高产率 (60-97%) 得到具有中等 ee (52-77%) . 通过 31P 和 1H NMR 光谱测量研究了机械洞察力。已通过分子内氢键稳定的关键烯醇中间体已通过 31P 和 1H NMR 光谱观
• Optically active phosphine derivative having at least two vinyl groups, polymer produced using the same as monomer, and transition metal complexes of these
  申请人：Takasago International Corporation

  公开号：US06248848B1

  公开（公告）日：2001-06-19

  A 2′-diarylphosphino-1,1′-biphenylen-2-yloxy(6,6′-divinyl-1,1′-binaphthalene-2,2′-diyloxy)phosphine derivative is disclosed, which is represented by general formula (I): wherein Ar is an optionally substituted phenyl or naphthyl; R1 and R2 each independently is a hydrogen atom, a lower alkyl, a lower alkoxy, etc.; and R3 is a lower alkyl, a lower alkoxy, etc.; provided that R2 and R3 may be bonded to each other to form a hydrocarbon ring, which may have one or more substituents selected from lower alkyl groups, halogen atoms, vinyl, etc. Also disclosed are a polymer having structural units derived from the phosphine derivative and a transition metal complex obtained by causing a transition metal compound to act on the phosphine derivative.

  本发明公开了一种2'-二芳基膦基-1,1'-联苯-2-氧基(6,6'-二乙烯基-1,1'-联萘-2,2'-二氧基)膦衍生物，其通式表示为(I)：其中Ar是可选取代的苯基或萘基；R1和R2各自独立地是氢原子、低碳基、低烷氧基等；R3是低碳基、低烷氧基等；前提是R2和R3可以结合形成碳氢环，该环可以有一个或多个取代基，所选取代基包括低碳基、卤素原子、乙烯基等。本发明还公开了一种由膦衍生物衍生的结构单元的聚合物以及通过使过渡金属化合物作用于膦衍生物而获得的过渡金属配合物。
• Optically active phosphine derivative having vinyl group, polymer
  申请人：Takasago International Corporation

  公开号：US06022936A1

  公开（公告）日：2000-02-08

  A 6-vinyl-2'-diarylphosphino-1,1'-binaphthalen-2-yloxy(biphenylene-2,2'-diyl oxy)phosphine derivative is disclosed, which is represented by general formula (I): ##STR1## wherein Ar is an optionally substituted phenyl or naphthyl; R.sup.1 and R.sup.2 each independently is a hydrogen atom, a lower alkyl, a lower alkoxy, etc.; and R.sup.3 is a lower alkyl, a lower alkoxy, etc.; provided that R.sup.2 and R.sup.3 may be bonded to each other to form a hydrocarbon ring, which may have one or more substituents selected from lower alkyl groups, halogen atoms, vinyl, etc. Also disclosed are a polymer having structural units derived from the phosphine derivative and a transition metal complex obtained by causing a transition metal compound to act on the phosphine derivative or the polymer. A novel polymer-supported ligand is provided which, when used as a catalyst for asymmetric syntheses, gives satisfactory results concerning catalytic activity, enantiomer excess, etc.

  本文披露了一种6-乙烯基-2'-二芳基膦基-1,1'-二萘-2-氧基（联苯-2,2'-二基氧）膦衍生物，其通式为（I）：##STR1## 其中Ar是可选择取代的苯基或萘基；R1和R2各自独立地是氢原子、低碳基、低烷氧基等；而R3是低碳基、低烷氧基等；但是，R2和R3可以连接在一起形成一个碳氢环，该环可以具有一个或多个选自低碳基团、卤素原子、乙烯等的取代基。此外，本文还披露了一种由膦衍生物结构单元衍生的聚合物以及通过将过渡金属化合物作用于膦衍生物或聚合物而获得的过渡金属配合物。本文还提供了一种新型聚合物支撑的配体，当用作不对称合成的催化剂时，可以得到令人满意的催化活性、对映异构体过量等结果。
• Optically active phosphine derivative having at least two vinyl groups,
  申请人：Takasago International Corporation

  公开号：US06143834A1

  公开（公告）日：2000-11-07

  A transition metal complex of a polymer of 2'-diarylphosphino-1,1'-biphenylen-2-yloxy(6,6'-divinyl-1,1'-binaphthalene -2,2'-diyloxy)phosphine derivative is disclosed, which is represented by general formula (I): ##STR1## wherein Ar is an optionally substituted phenyl or naphthyl; R.sup.1 and R.sup.2 each independently is a hydrogen atom, a lower alkyl, a lower alkoxy, etc.; and R.sup.3 is a lower alkyl, a lower alkoxy, etc.; provided that R.sup.2 and R.sup.3 may be bonded to each other to form a hydrocarbon ring, which may have one or more substituents selected from lower alkyl groups, halogen atoms, vinyl, etc. Also disclosed are a polymer having structural units derived from the phosphine derivative and a transition metal complex obtained by causing a transition metal compound to act on the phosphine derivative or the polymer. A novel polymer-supported ligand is provided which, when used as a catalyst for asymmetric syntheses, gives satisfactory results concerning catalytic activity, enantiomer excess, etc.

  本发明揭示了一种2'-二芳基膦基-1,1'-联苯并-2-氧基(6,6'-二乙烯基-1,1'-联萘并-2,2'-二氧基)膦衍生物的聚合物的过渡金属配合物，其通式表示为(I)：##STR1## 其中Ar是可选取代的苯基或萘基；R.sup.1和R.sup.2各自独立地是氢原子、低碳基、低烷氧基等；R.sup.3是低碳基、低烷氧基等；前提是R.sup.2和R.sup.3可以连接在一起形成一个碳氢环，该碳氢环可以具有一个或多个从低碳基团、卤素原子、乙烯等中选择的取代基。还揭示了一种由膦衍生物衍生的结构单元的聚合物以及通过使过渡金属化合物作用于膦衍生物或聚合物而获得的过渡金属配合物。提供了一种新型的聚合物支持的配体，当用作不对称合成的催化剂时，具有令人满意的催化活性、对映异构体过量等结果。
• Optically active phosphine derivative having vinyl group, polymer produced using the same as monomer and transition metal complexes of these
  申请人：Takasago International Corporation

  公开号：EP0877029A2

  公开（公告）日：1998-11-11

  A 6-vinyl-2'-diarylphosphino-1,1'-binaphthalen-2-yloxy(biphenylene-2,2'-diyloxy)phosphine derivative is disclosed, which is represented by general formula (I): wherein Ar is an optionally substituted phenyl or naphthyl; R1 and R2 each independently is a hydrogen atom, a lower alkyl, a lower alkoxy, etc.; and R3 is a lower alkyl, a lower alkoxy, etc.; provided that R2 and R3 may be bonded to each other to form a hydrocarbon ring, which may have one or more substituents selected from lower alkyl groups, halogen atoms, vinyl, etc. Also disclosed are a polymer having structural units derived from the phosphine derivative and a transition metal complex obtained by causing a transition metal compound to act on the phosphine derivative or the polymer. A novel polymer-supported ligand is provided which, when used as a catalyst for asymmetric syntheses, gives satisfactory results concerning catalytic activity, enantiomer excess, etc.

  本发明公开了一种 6-乙烯基-2'-二基膦-1,1'-联萘-2-氧基(联苯-2,2'-二氧基)膦衍生物，由通式(I)表示： 其中 Ar 是任选取代的苯基或萘基；R1 和 R2 各自独立地是氢原子、低级烷基、低级烷氧基等；R3 是低级烷基、低级烷氧基等；条件是 R2 和 R3 可相互键合形成烃环，该烃环可具有一个或多个选自低级烷基、卤素原子、乙烯基等的取代基。还公开了一种聚合物，其结构单元来源于膦衍生物，以及通过使过渡金属化合物作用于膦衍生物或聚合物而获得的过渡金属配合物。本发明提供了一种新型聚合物支撑配体，该配体用作不对称合成的催化剂时，可在催化活性、对映体过量等方面获得令人满意的结果。