(+/-)-3,3'-dichloro-6-(diphenylphosphinyo)-2,2',4,4'-tetramethyl-6'-<<(trifluoromethyl)sulfonyl>oxy>biphenyl | 205375-80-0

• 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: (+/-)-3,3'-dichloro-6-(diphenylphosphinyo)-2,2',4,4'-tetramethyl-6'-<<(trifluoromethyl)sulfonyl>oxy>biphenyl
• 英文别名: (R)-(+)-2-diphenylphosphinyl-2'-(trifluoromethanesulfonyloxy)-5,5'-dichloro-4,4',6,6'-tetramethyl-1,1'-biphenyl；[4-Chloro-2-(3-chloro-6-diphenylphosphoryl-2,4-dimethylphenyl)-3,5-dimethylphenyl] trifluoromethanesulfonate
• CAS: 205375-80-0；155566-48-6
• 化学式: C₂₉H₂₄Cl₂F₃O₄PS
• 分子量: 627.448
• InChiKey: GPGLCPKTXZPYEY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  40
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (+/-)-3,3'-dichloro-6-(diphenylphosphinyo)-2,2',4,4'-tetramethyl-6'-<<(trifluoromethyl)sulfonyl>oxy>biphenyl 在 lithium hydroxide 、 三氯硅烷 、 三乙胺 作用下， 生成 4-chloro-2-(3-chloro-6-diphenylphosphoryl-2,4-dimethylphenyl)-3,5-dimethylphenol
  参考文献：
  名称：

  Synthesis of new chiral phosphinephosphites having 2-diphenylphosphinobiphenyl-2′-yl backbone and their use in Rh(I)-catalyzed asymmetric hydroformylations

  摘要：

  New chiral phosphinephosphites (R)-(5,5'-dichloro-2-diphenylphosphino-4,4',6,6'-tetramethylbiphenyl-2'-yl)((S)-1,1'-binaphthalen-2,2'-diyl)phosphite [abbreviated (R,S)-BIPHEMPHOS] and its enantiomer (S,R)-BIPHEMPHOS have been synthesized from 5,5'-dichloro-4,4',6,6'-tetramethyl-2,2'-biphenyldiol in enantiomerically pure form. Their Rh(I) complexes have been shown to be highly efficient catalysts for asymmetric hydroformylations of a variety of olefinic substrates. The corresponding phosphinephosphites derived from 2,2'-biphenyldiol were also tested as ligands for asymmetric hydroformylation.

  DOI：

  10.1016/s0040-4039(00)73039-5
• 作为产物：
  描述：

  4-氯-3,5-二甲基苯酚 在 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 diacetyl [1,3-bis(diphenylphosphine)propane]palladium 、 三氯化铁 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 生成 (+/-)-3,3'-dichloro-6-(diphenylphosphinyo)-2,2',4,4'-tetramethyl-6'-<<(trifluoromethyl)sulfonyl>oxy>biphenyl
  参考文献：
  名称：

  Synthesis of new chiral phosphinephosphites having 2-diphenylphosphinobiphenyl-2′-yl backbone and their use in Rh(I)-catalyzed asymmetric hydroformylations

  摘要：

  New chiral phosphinephosphites (R)-(5,5'-dichloro-2-diphenylphosphino-4,4',6,6'-tetramethylbiphenyl-2'-yl)((S)-1,1'-binaphthalen-2,2'-diyl)phosphite [abbreviated (R,S)-BIPHEMPHOS] and its enantiomer (S,R)-BIPHEMPHOS have been synthesized from 5,5'-dichloro-4,4',6,6'-tetramethyl-2,2'-biphenyldiol in enantiomerically pure form. Their Rh(I) complexes have been shown to be highly efficient catalysts for asymmetric hydroformylations of a variety of olefinic substrates. The corresponding phosphinephosphites derived from 2,2'-biphenyldiol were also tested as ligands for asymmetric hydroformylation.

  DOI：

  10.1016/s0040-4039(00)73039-5

文献信息

• Highly Enantioselective Hydroformylation of Olefins Catalyzed by Rhodium(I) Complexes of New Chiral Phosphine−Phosphite Ligands
  作者：Kyoko Nozaki、Nozomu Sakai、Tetsuo Nanno、Takanori Higashijima、Satoshi Mano、Toshihide Horiuchi、Hidemasa Takaya

  DOI：10.1021/ja970049d

  日期：1997.5.1

  1‘-binaphthalen-2‘-yl (S)-1,1‘-binaphthalene-2,2‘-diyl phosphite [(R,S)-BINAPHOS, (R,S)-2a], was synthesized. Its Rh(I) complex was prepared, and its structure has been characterized by 1H and 31P NMR spectroscopy. Using Rh(I) complexes of (R,S)-2a and its enantiomer, highly enantioselective hydroformylation of styrene has been performed (94% ee, iso/normal = 88/12). The catalyst system was also effective

  一种新的手性膦-亚磷酸酯配体，(R)-2-(diphenylphosphino)-1,1'-binaphthalen-2'-yl (S)-1,1'-binaphthalene-2,2'-diyl phosphite [(R ,S)-BINAPHOS, (R,S)-2a]，合成。制备了其Rh(I)配合物，并通过1H和31P NMR光谱对其结构进行了表征。使用 (R,S)-2a 及其对映异构体的 Rh(I) 配合物，已经进行了苯乙烯的高度对映选择性加氢甲酰化 (94% ee, 异/正 = 88/12)。该催化剂体系对多种其他烯烃也有效。其他一些带有 1,1'-联萘和联苯骨架的膦-亚磷酸酯配体，例如 (S)-3,3'-dichloro-6-(diphenylphosphino)-2,2',4,4'-tetramethylbiphenyl-6' -yl (R)-1,1'-联萘-2,2'-二基亚磷酸酯
• Optically active diphosphine compound, method for making the compound,
  申请人：Takasago International Corporation

  公开号：US05847222A1

  公开（公告）日：1998-12-08

  The present invention provides a ligand for a novel catalyst superior in such characteristics as selectivity (chemoselectivity and enantioselectivity) and catalytic activity in asymmetric synthesis reactions and a ligand for a novel catalyst effective in an asymmetric hydrogenation reaction in particular. The ligand is an optically active diphosphine compound represented by the following formula: ##STR1## where Ph is a phenyl group, X is a chlorine or bromine atom, and R.sup.1 and R.sup.2 are each an alkyl group having 1 to 3 carbon atoms.

  本发明提供了一种新型催化剂的配体，其具有选择性（化学选择性和对映选择性）和催化活性等特性优越，在不对称合成反应中特别有效的一种新型催化剂的配体。该配体是一种光学活性的二膦化合物，其化学式如下：##STR1## 其中，Ph是苯基，X是氯或溴原子，R.sup.1和R.sup.2分别是具有1至3个碳原子的烷基基团。
• Phosphine compounds, complexes containing the phosphine compounds as ligands, process for producing optically active aldehydes using the phosphine compounds, or complexes, and 4-[(R)-1' formylethyl]azetidin-2-one derivatives
  申请人：Takasago International Corporation

  公开号：EP0614903A2

  公开（公告）日：1994-09-14

  Novel phosphine compounds are represented by formulae (I) and (II): wherein the R substituents have the significations defined in the specification and are useful in the form of their transition metal complexes, or of compounds with transition metals, in producing an optically active aldehyde by hydroformylation of an olefin with high positional and steric selectivities. A 4-[(R)-1'-formylethyl]azetidin-2-one derivative obtainable by the process is particularly useful as an intermediate for the preparation of carbapenem antibiotics.

  新颖的膦化合物由式 (I) 和 (II) 表示： 其中 R 取代基具有说明书中定义的含义，以其过渡金属络合物或与过渡金属的化合物的形式，通过烯烃的氢甲酰化生产光学活性醛，具有高位置选择性和立体选择性。通过该工艺获得的 4-[(R)-1'-甲酰基乙基]氮杂环丁烷-2-酮衍生物尤其可用作制备碳青霉烯类抗生素的中间体。
• Phosphine compounds, complexes containing the phosphine compounds as ligands, and process for producing optically active aldehydes using the phosphine compounds or complexes
  申请人：Takasago International Corporation

  公开号：EP0684249A1

  公开（公告）日：1995-11-29

  Novel phosphine compounds are represented by formulae (I) and (II): wherein the R substituents have the significations defined in the specification and are useful in the form of their transition metal complexes, or of compounds with transition metals, in producing an optically active aldehyde by hydroformylation of an olefin with high positional and steric selectivities.

  新颖的膦化合物由式 (I) 和 (II) 表示： 其中 R 取代基具有说明书中定义的含义，以其过渡金属络合物或与过渡金属的化合物的形式，通过烯烃的氢甲酰化反应生产光学活性醛时，具有高位置选择性和立体选择性。
• Higashizima Takanori, Sakai Nozomu, Nozaki Kyoko, Takaya Hidemasa, Tetrahedron Lett, 35 (1994) N 13, S 2023-2026
  作者：Higashizima Takanori, Sakai Nozomu, Nozaki Kyoko, Takaya Hidemasa

  DOI：——

  日期：——