(R)-(-)-2-acetylamino-2'-diphenylphosphinyl-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-acetylamino-2'-diphenylphosphinyl-1,1'-binaphthyl
• 英文别名: (R)-(-)-2-(acetamido)-2'-(diphenylphosphinoyl)-1,1'-binaphthyl；N-[1-(2-Diphenylphosphorylnaphthalen-1-yl)naphthalen-2-yl]acetamide
• 化学式: C₃₄H₂₆NO₂P
• 分子量: 511.56
• InChiKey: HLLHVPDMPHIELI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  38
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.03
• 拓扑面积：
  46.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  (R)-2′-hydroxy-(1,1′-binaphthalen)-2-yl trifluoromethanesulfonate 在 吡啶 、 盐酸 、 20 % Pd(OH)2/C 、 palladium diacetate 、 sodium hydride 、 caesium carbonate 、 溶剂黄146 、 1,4-双(二苯基膦)丁烷 、 双(2-二苯基磷苯基)醚 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 氯仿 、 甲苯 为溶剂， 反应 16.0h， 生成 (R)-(-)-2-acetylamino-2'-diphenylphosphinyl-1,1'-binaphthyl
  参考文献：
  名称：

  多功能手性膦催化森田-的Baylis-希尔曼加合物的高度非对映和不对称取代恶唑酮与†

  摘要：

  多功能手性膦（膦–硫脲类型）在恶性条件下L2催化的MBH加合物1被恶唑酮2的烯丙基取代产生相应的旋光加合物3，良好至极佳的收率和ee，以及中等至良好的de。已经讨论了氢键供体位点和亲核位点之间的协同相互作用，这表明微调多功能膦有机催化剂的活性位非常重要。

  DOI：

  10.1039/c1ob00017a

文献信息

• Multifunctional chiral phosphines-catalyzed highly diastereoselective and enantioselective substitution of Morita–Baylis–Hillman adducts with oxazolones
  作者：Yuan-Liang Yang、Cheng-Kui Pei、Min Shi

  DOI：10.1039/c1ob00017a

  日期：——

  Multifunctional chiral phosphine (phosphine–thiourea type) L2-catalyzed allylic substitutions of MBH adducts 1 with oxazolones 2 produce the corresponding optically active adducts 3 in good to excellent yields and ee's as well as moderate to good de's under mild conditions. The synergistic interaction between hydrogen bond donor site and nucleophilic site has been discussed, indicating that finely

  多功能手性膦（膦–硫脲类型）在恶性条件下L2催化的MBH加合物1被恶唑酮2的烯丙基取代产生相应的旋光加合物3，良好至极佳的收率和ee，以及中等至良好的de。已经讨论了氢键供体位点和亲核位点之间的协同相互作用，这表明微调多功能膦有机催化剂的活性位非常重要。
• 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。
• Ligands based on chiral 2-amino-2′-hydroxy-1,1′-binaphthyl and related frameworks for asymmetric catalysis
  申请人：The Penn State Research Foundation

  公开号：US06380392B1

  公开（公告）日：2002-04-30

  The present invention includes array of new chiral ligands that are optically active or racemic. These ligands are bidentate, tridentate, tetradentate or pentadentate ligands which include P-P, P-N, N-N, mixed P-N, Schiff base or carbene sites. The present invention further includes a catalyst prepared by a process, which includes contacting a transition metal salt, or a complex thereof, and a ligand according to the present invention. The present invention still further includes a process for preparation of an asymmetric compound. In this process, a substrate capable of forming an asymmetric product by an asymmetric reaction and a catalyst according to the present invention are contacted to produce an asymmetric product. Transition metal complexes with these ligands are effective catalysts for asymmetric reactions. Applicant has discovered that asymmetric products can be prepared using the chiral catalysts according to the present invention in enantioselective reactions, such as hydrogenation, hydroformylation, Michael addition, Heck reaction, Aldol reaction, allylic alkylation, cyclopropanation, epoxidation, and olefin metathesis.

  本发明包括一系列新的手性配体阵列，这些配体具有光学活性或消旋性。这些配体是双齿、三齿、四齿或五齿配体，包括P-P、P-N、N-N、混合P-N、席夫碱基或卡宾位点。本发明还包括通过一种过程制备的催化剂，该过程包括将一种过渡金属盐或其复合物与本发明的配体接触。本发明还进一步包括一种制备不对称化合物的方法。在这个过程中，通过不对称反应能够形成不对称产物的底物与根据本发明的催化剂接触，从而产生不对称产物。具有这些配体的过渡金属配合物是对不对称反应有效的催化剂。申请人发现，可以使用根据本发明的手性催化剂在对映选择性反应中制备不对称产物，例如氢化、氢甲酰化、迈克尔加成、赫克反应、阿尔多尔反应、烯丙基烷基化、环丙烷化、环氧化和烯烃交换反应。
• 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。