(R)-(-)-2-(ethylamino)-2'-(diphenylphosphino)-1,1'-binaphthyl

• 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-(ethylamino)-2'-(diphenylphosphino)-1,1'-binaphthyl
• 英文别名: (R)-(-)-2-ethylamino-2'-diphenylphosphino-1,1'-binaphthyl；1-(2-diphenylphosphanylnaphthalen-1-yl)-N-ethylnaphthalen-2-amine
• 化学式: C₃₄H₂₈NP
• 分子量: 481.577
• InChiKey: NTEPSANRAKAWDQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  36
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.06
• 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：

  3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl phosphorochloridite 、 (R)-(-)-2-(ethylamino)-2'-(diphenylphosphino)-1,1'-binaphthyl 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.0h， 以52%的产率得到2,4,8,10-tetratert-butyl-N-[1-(2-diphenylphosphanylnaphthalen-1-yl)naphthalen-2-yl]-N-ethylbenzo[d][1,3,2]benzodioxaphosphepin-6-amine
  参考文献：
  名称：

  非对称羰基化反应中模块化膦-亚磷酰胺配体的合成与应用：结构-选择性关系

  摘要：

  通过手性BINOL（1,1'-bi-2-萘酚）或NOBIN（2-amino-2'-hydroxy-1,1'-binaphthyl）设计并合成了一系列杂化膦-亚磷酰胺配体。他们在苯乙烯衍生物（支链/线性比高达56.6，ee高达99％），乙酸乙烯酯衍生物（高达ee高达98％）和烯丙基氰化物（高达RH）的Rh催化的不对称加氢甲酰化反应中获得了很高的区域和对映选择性。96％ee）。配体结构的系统变化表明，亚铁酰胺部分上的空间因子决定了配体的性能。随着障碍的增加，支链/线性比率上升，而ee苯乙烯的加氢甲酰化过程中的分子量值下降。但是，N取代基对选择性的影响不大。

  DOI：

  10.1002/chem.200902238
• 作为产物：
  描述：

  (R)-(-)-2-acetylamino-2'-diphenylphosphinyl-1,1'-binaphthyl 在 dimethyl sulfide borane 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以76%的产率得到(R)-(-)-2-(ethylamino)-2'-(diphenylphosphino)-1,1'-binaphthyl
  参考文献：
  名称：

  Efficient synthesis of optically active 2-amino-2'-diphenylphosphino-1,1'-binaphthyl and its derivatives

  摘要：

  具有各种官能团的具有光学活性的2-氨基-2'-二苯基磷酰基-1,1'-联萘，例如氨基，烷氧羰基氨基，酰胺基，单烷基和双烷基氨基，以及C2位置的磺酰胺基被制备。上述氨基磷酸酯的关键中间体是由具有光学活性的2-氰基-2'-二苯基磷酰基-1,1'-联萘合成的2-氨基甲酰基-2'-二苯基磷酰基-1,1'-联萘。将甲酰基转化为氨基是通过Hofmann反应实现的。关键词：氨基磷酸酯配体，Hofmann反应，光学活性磷酸酯配体。

  DOI：

  10.1139/v99-248

文献信息

• Efficient synthesis of optically active 2-amino-2'-diphenylphosphino-1,1'-binaphthyl and its derivatives
  作者：Kenzo Sumi、Takao Ikariya、Ryoji Noyori

  DOI：10.1139/v99-248

  日期：2000.6.1

  Optically active 2-amino-2'-diphenylphosphino-1,1'-binaphthyls having various functional groups, such as amino, alkoxycarbonylamino, acylamino, mono- and dialkylamino, and sulfonylamino at C2 position were prepared. The key intermediate of the above aminophosphines was 2-carbamoyl-2'-diphenylphosphinyl-1,1'-binaphthyl synthesized from optically active 2-cyano-2'-diphenylphosphinyl-1,1'-binaphthyl. The transformation of the carbamoyl group to an amino group was effected by the Hofmann reaction.Key words: aminophosphine ligand, Hofmann reaction, optically active phosphine ligand.

  具有各种官能团的具有光学活性的2-氨基-2'-二苯基磷酰基-1,1'-联萘，例如氨基，烷氧羰基氨基，酰胺基，单烷基和双烷基氨基，以及C2位置的磺酰胺基被制备。上述氨基磷酸酯的关键中间体是由具有光学活性的2-氰基-2'-二苯基磷酰基-1,1'-联萘合成的2-氨基甲酰基-2'-二苯基磷酰基-1,1'-联萘。将甲酰基转化为氨基是通过Hofmann反应实现的。关键词：氨基磷酸酯配体，Hofmann反应，光学活性磷酸酯配体。
• Complexes of transition metals with novel axial asymmetric compounds as the ligands
  申请人：Takasago International Corporation

  公开号：US06323353B1

  公开（公告）日：2001-11-27

  The invention provides a metal complex comprising a ligand and a metal. The ligand is an aminophosphine compound represented by the following formula (1) The metal is rhodium, ruthenium, iridium or nickel.

  该发明提供了一种包括配体和金属的金属配合物。该配体是一种由以下化学式（1）表示的氨基膦化合物。金属是铑、钌、铱或镍。
• Method for producing axial asymmetric compounds, intermediates for producing the same, complexes of transition metals with novel axial asymmetric compounds as the ligands, catalysts for asymmetric hydrogenation, and catalysts for forming asymmetric carbon-carbon bonds
  申请人：Takasago International Corporation

  公开号：US20010047110A1

  公开（公告）日：2001-11-29

  The invention provides a metal complex comprising a ligand and a metal. The ligand is an aminophosphine compound represented by the following formula (1) 1 [Each Ar represents an aryl group optionally substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, both Ar's being same or different with each other. R 1 and R 2 represent hydrogen atom, a cycloalkyl group having 5 to 7 carbon atoms, or an alkyl group having 1 to 6 carbon atom optionally substituted with a halogen atom, a lower alkoxy group or phenyl group, with R 1 and R 2 being same or different with each other. Alternatively, one of R 1 and R 2 is hydrogen atom and the other is —COR 3 (R 3 represents a cycloalkyl group having 5 to 7 carbon atoms, a lower alkyl group having 1 to 6 carbon atom optionally substituted with a halogen atom, a lower alkoxy group or phenyl group, a substituted or unsubstituted phenyl group, or a lower alkoxy group having 1 to 6 carbon atom optionally substituted with a cycloalkyl group having 5 to 7 carbon atoms, a halogen atom, a lower alkoxy group or phenyl group) or —SO 2 R 4 (R 4 represents a cycloalkyl group having 5 to 7 carbon atoms, an alkyl group optionally substituted with a halogen atom, a lower alkoxy group or phenyl group, or substituted or unsubstituted phenyl group). n represents 0]. The metal is rhodium, ruthenium, iridium or nickel.

  本发明提供了一种包含配体和金属的金属配合物。该配体是由以下式子（1）表示的氨基膦化合物组成：1[每个Ar代表一个芳基基团，可以选择地用卤原子、具有1到4个碳原子的较低烷基基团或烷氧基取代，两个Ar相同或不同。R1和R2代表氢原子，具有5到7个碳原子的环烷基团或具有1到6个碳原子的烷基基团，可以选择地用卤原子、较低烷氧基或苯基取代，其中R1和R2相同或不同。或者，R1和R2中的一个是氢原子，另一个是-COR3（R3代表具有5到7个碳原子的环烷基团、具有1到6个碳原子的较低烷基基团，可以选择地用卤原子、较低烷氧基或苯基取代，取代或未取代的苯基或具有5到7个碳原子的环烷基团、卤原子、较低烷氧基或苯基取代的具有1到6个碳原子的较低烷氧基）或-SO2R4（R4代表具有5到7个碳原子的环烷基团、可以选择地用卤原子、较低烷氧基或苯基取代的烷基，或取代或未取代的苯基）。n代表0。金属是铑、钌、铱或镍。
• METHOD FOR PRODUCING AXIAL ASYMMETRIC COMPOUNDS, INTERMEDIATES FOR PRODUCING THE SAME, COMPLEXES OF TRANSITION METALS WITH NOVEL AXIAL ASYMMETRIC COMPOUNDS AS THE LIGANDS, CATALYSTS FOR ASYMMETRIC HYDROGENATION, AND CATALYSTS FOR FORMING ASYMMETRIC CARBON-CARBON BONDS
  申请人：Takasago International Corporation

  公开号：US06515156B2

  公开（公告）日：2003-02-04

  The invention provides a metal complex comprising a ligand and a metal. The ligand is an aminophosphine compound represented by the following formula (1) [Each Ar represents an aryl group optionally substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, both Ar's being same or different with each other. R1 and R2 represent hydrogen atom, a cycloalkyl group having 5 to 7 carbon atoms, or an alkyl group having 1 to 6 carbon atom optionally substituted with a halogen atom, a lower alkoxy group or phenyl group, with R1 and R2 being same or different with each other. Alternatively, one of R1 and R2 is hydrogen atom and the other is —COR3 (R3 represents a cycloalkyl group having 5 to 7 carbon atoms, a lower alkyl group having 1 to 6 carbon atom optionally substituted with a halogen atom, a lower alkoxy group or phenyl group, a substituted or unsubstituted phenyl group, or a lower alkoxy group having 1 to 6 carbon atom optionally substituted with a cycloalkyl group having 5 to 7 carbon atoms, a halogen atom, a lower alkoxy group or phenyl group) or —SO2R4 (R4 represents a cycloalkyl group having 5 to 7 carbon atoms, an alkyl group optionally substituted with a halogen atom, a lower alkoxy group or phenyl group, or substituted or unsubstituted phenyl group). n represents 0]. The metal is rhodium, ruthenium, iridium or nickel.

  本发明提供了一种包含配体和金属的金属配合物。该配体是一种氨基膦化合物，由以下式子（1）表示：[每个Ar代表一个芳基，可选地取代有卤素原子、具有1至4个碳原子的低烷基或烷氧基，其中两个Ar相同或不同。R1和R2代表氢原子、具有5至7个碳原子的环烷基或具有1至6个碳原子的烷基，可选地取代有卤素原子、低烷氧基或苯基，其中R1和R2相同或不同。或者，R1和R2中的一个是氢原子，另一个是-COR3（其中R3代表具有5至7个碳原子的环烷基、具有1至6个碳原子的低烷基，可选地取代有卤素原子、低烷氧基或苯基、取代或未取代的苯基，或具有5至7个碳原子的环烷基、卤素原子、低烷氧基或苯基可选地取代有1至6个碳原子的低烷氧基）或-SO2R4（其中R4代表具有5至7个碳原子的环烷基、可选地取代有卤素原子、低烷氧基或苯基的烷基，或取代或未取代的苯基）。n代表0]。金属是铑、钌、铱或镍。
• Aminophosphine-metal complex for asymmetric reactions
  申请人：Takasago International Corporation

  公开号：EP1013658A1

  公开（公告）日：2000-06-28

  The invention provides a metal complex comprising a ligand and a metal. The ligand is an aminophosphine compound represented by the following formula (1) [Each Ar represents an aryl group optionally substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, both Ar's being same or different with each other. R1 and R2 represent hydrogen atom, a cycloalkyl group having 5 to 7 carbon atoms, or an alkyl group having 1 to 6 carbon atom optionally substituted with a halogen atom, a lower alkoxy group or phenyl group, with R1 and R2 being same or different with each other. Alternatively, one of R1 and R2 is hydrogen atom and the other is -COR3 (R3 represents a cycloalkyl group having 5 to 7 carbon atoms, a lower alkyl group having 1 to 6 carbon atom optionally substituted with a halogen atom, a lower alkoxy group or phenyl group, a substituted or unsubstituted phenyl group, or a lower alkoxy group having 1 to 6 carbon atom optionally substituted with a cycloalkyl group having 5 to 7 carbon atoms, a halogen atom, a lower alkoxy group or phenyl group) or -SO2R4 (R4 represents a cycloalkyl group having 5 to 7 carbon atoms, an alkyl group optionally substituted with a halogen atom, a lower alkoxy group or phenyl group, or substituted or unsubstituted phenyl group). n represents 0]. The metal is rhodium, ruthenium, iridium or nickel.

  本发明提供了一种由配体和金属组成的金属配合物。配体是由下式（1）表示的氨基膦化合物 [每个 Ar 代表一个芳基，可任选被一个卤素原子、一个具有 1 至 4 个碳原子的低级烷基或一个烷氧基取代，两个 Ar 彼此相同或不同。R1 和 R2 代表氢原子、具有 5 至 7 个碳原子的环烷基或具有 1 至 6 个碳原子的烷基，可选择被卤素原子、低级烷氧基或苯基取代，R1 和 R2 彼此相同或不同。或者，R1 和 R2 中的一个是氢原子，另一个是-COR3（R3 代表具有 5 至 7 个碳原子的环烷基、具有 1 至 6 个碳原子且任选被卤素原子取代的低级烷基、低级烷氧基或苯基、取代或未取代的苯基、或具有 1 至 6 个碳原子的低级烷氧基，可选择被具有 5 至 7 个碳原子的环烷基、卤素原子、低级烷氧基或苯基取代）或 -SO2R4 （R4 代表具有 5 至 7 个碳原子的环烷基、可选择被卤素原子取代的烷基、低级烷氧基或苯基、取代或未取代的苯基）。n 代表 0]。金属是铑、钌、铱或镍。