(R)-(-)-2,2'-bis(trifluoromethanesulfonyloxy)-5,5'-dichloro-4,4',6,6'-tetramethyl-1,1'-biphenyl | 205375-79-7

• 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)-(-)-2,2'-bis(trifluoromethanesulfonyloxy)-5,5'-dichloro-4,4',6,6'-tetramethyl-1,1'-biphenyl
• 英文别名: (+/-)-5,5'-dichloro-4,4',6,6'-tetramethyl-2,2'-bis<<(trifluoromethyl)sulfonyl>oxy>biphenyl；3,3'-Dichloro-2,2',4,4'-tetramethyl-6,6'-bis(trifluoromethanesulfonyloxy)biphenyl；(+/-)-3,3'-Dichloro-2,2',4,4'-tetramethyl-6,6'-bis(trifluoromethanesulfonyloxy)biphenyl；[4-Chloro-2-[3-chloro-2,4-dimethyl-6-(trifluoromethylsulfonyloxy)phenyl]-3,5-dimethylphenyl] trifluoromethanesulfonate
• CAS: 205375-79-7；155566-47-5
• 化学式: C₁₈H₁₄Cl₂F₆O₆S₂
• 分子量: 575.334
• InChiKey: WYBUJDNBXZTDJL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  34
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  (R)-(-)-2,2'-bis(trifluoromethanesulfonyloxy)-5,5'-dichloro-4,4',6,6'-tetramethyl-1,1'-biphenyl 在 lithium hydroxide 、 diacetyl [1,3-bis(diphenylphosphine)propane]palladium 、 三氯硅烷 、 三乙胺 、 N,N-二异丙基乙胺 作用下， 以 二甲基亚砜 为溶剂， 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 、 三氯化铁 作用下， 以 二氯甲烷 为溶剂， 生成 (R)-(-)-2,2'-bis(trifluoromethanesulfonyloxy)-5,5'-dichloro-4,4',6,6'-tetramethyl-1,1'-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

• Phosphine compound, complex containing the phosphine compound as ligand,
  申请人：Takasago International Corporation

  公开号：US05530150A1

  公开（公告）日：1996-06-25

  A phosphine compound represented by one of the formulas: ##STR1## wherein R.sup.1 and R.sup.2, which may be the same or different, each represent a phenyl group or a phenyl group substituted with a halogen atom or a lower alkyl group or taken together form a divalent hydrocarbon group; and R.sup.3 and R.sup.4, which may be the same or different, each represent a lower alkyl group, a phenyl group or a phenyl group substituted with a halogen atom, a lower alkyl group or a lower alkoxy group or taken together form a divalent hydrocarbon group, and wherein R.sup.6 and R.sup.6' which may be the same or different, each represent a hydrogen atom, a lower alkyl group or a lower alkoxy group; R.sup.5, R.sup.5', R.sup.11 and R.sup.11' which may be the same or different, each represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom; or a pair of R.sup.5 and R.sup.6 or a pair of R.sup.5' and R.sup.6' may form a ring; R.sup.7 and R.sup.8, which may be the same or different, each represent a phenyl group or a phenyl group substituted with a lower alkyl group, a halogen atom or a lower alkoxy group; and R.sup.9 and R.sup.10, which may be the same or different, each represent a phenyl group or a phenyl group substituted with a lower alkyl group, a lower alkoxy group or a halogen atom; or R.sup.9 and R.sup.10 may be taken together to form a divalent hydrocarbon group.

  一种磷化氢化合物，可以用以下公式之一表示：##STR1## 其中，R.sup.1和R.sup.2可以相同或不同，每个代表一个苯基团或一个被卤素原子或低级烷基团取代的苯基团，或者共同形成一个二价碳氢化合物团；R.sup.3和R.sup.4可以相同或不同，每个代表一个低级烷基团、一个苯基团或一个被卤素原子、低级烷基团或低级烷氧基团取代的苯基团，或者共同形成一个二价碳氢化合物团；R.sup.6和R.sup.6'可以相同或不同，每个代表一个氢原子、一个低级烷基团或一个低级烷氧基团；R.sup.5、R.sup.5'、R.sup.11和R.sup.11'可以相同或不同，每个代表一个氢原子、一个低级烷基团、一个低级烷氧基团或一个卤素原子；或者R.sup.5和R.sup.6的一对或R.sup.5'和R.sup.6'的一对可以形成一个环；R.sup.7和R.sup.8可以相同或不同，每个代表一个苯基团或一个被低级烷基团、卤素原子或低级烷氧基团取代的苯基团；R.sup.9和R.sup.10可以相同或不同，每个代表一个苯基团或一个被低级烷基团、低级烷氧基团或卤素原子取代的苯基团；或者R.sup.9和R.sup.10可以共同形成一个二价碳氢化合物团。
• 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。