(R)-(+)-2-carbamoyl-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-carbamoyl-2'-diphenylphosphinyl-1,1'-binaphthyl
• 英文别名: 1-(2-diphenylphosphorylnaphthalen-1-yl)naphthalene-2-carboxamide
• 化学式: C₃₃H₂₄NO₂P
• 分子量: 497.533
• InChiKey: NMEIWYVBRAOXPH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  37
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  60.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-(+)-2-carbamoyl-2'-diphenylphosphinyl-1,1'-binaphthyl 在 甲醇 、 氢氧化钾 、 溴 作用下， 以 1,4-二氧六环 、 甲醇 为溶剂， 反应 5.0h， 生成 (R)-(-)-2-amino-2'-diphenylphosphinyl-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：

  diphenylphosphine oxide 在 sodium hydroxide 、 三氟甲磺酸酐 、 双氧水 作用下， 以 乙醇 为溶剂， 反应 24.0h， 生成 (R)-(+)-2-carbamoyl-2'-diphenylphosphinyl-1,1'-binaphthyl
  参考文献：
  名称：

  A new chiral 2-sulfonylamino-2′-phosphino-1,1′-binaphthyl ligand for highly enantioselective copper-catalyzed conjugate addition of diethylzinc to benzylideneacetones

  摘要：

  A new axially chiral phosphine-sulfonamide ligand was prepared via a chiral component (R)-2-amino-2'-diphenyl-phosphinyl-1,1'-binaphthyl, which was conveniently synthesized through a new route involving hydrolysis of (R)-2-cyano-2'-phosphinyl-1,1'-binaphthyl followed by Hofmann rearrangement of the amide group. The new ligand was found to be very efficient in copper-catalyzed enantio selective conjugate addition of diethylzinc to acyclic enones such as benzylideneacetones, providing very high enantioselectivity up to 99% ee. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.05.101

文献信息

• Chiral Phosphine-Catalyzed Enantioselective Construction of γ-Butenolides Through Substitution of Morita−Baylis−Hillman Acetates with 2-Trimethylsilyloxy Furan
  作者：Ying-Qing Jiang、Yong-Ling Shi、Min Shi

  DOI：10.1021/ja802422d

  日期：2008.6.1

  Chiral multifunctional phosphine (R)-N-(2'-diphenylphosphanyl-[1,1']binaphthalenyl-2-yl)methanesulfonamide L2 or (R)-N-(2'-diphenylphosphanyl-[1,1']binaphthalenyl-2-yl)acetamide L3 is an efficient catalyst in the allylic substitutions of MBH acetates 1 with 2-trimethylsilyloxy furan 2 to provide gamma-butenolides 3 in good to excellent yields and enantiomeric excesses in the presence of water.

  手性多功能膦 (R)-N-(2'-二苯基膦酰基-[1,1']联萘基-2-基)甲磺酰胺 L2 或 (R)-N-(2'-二苯基膦酰基-[1,1']联萘基- 2-基）乙酰胺 L3 是 MBH 乙酸酯 1 与 2-三甲基甲硅烷氧基呋喃 2 烯丙基取代的有效催化剂，以在水存在下以良好至极好的产率和对映体过量提供 γ-丁烯内酯 3。
• Synthetic Access to a Novel Binaphthyl Ligand Bearing a Phosphine and a Triazole Donor Site
  作者：Claudia May、Yu Sun、Gotthelf Wolmershäuser、Werner R. Thiel

  DOI：10.1515/znb-2009-11-1226

  日期：2009.12.1

  The combination of a diphenylphospinyl and a triazol-3-yl unit was realized for the first time at a 1,1'-binaphthyl backbone. This novel type of P,N-ligand is accessible as an enantiomerically pure compound in just a few steps. First experiments on the coordination chemistry with palladium(II) chloride have been carried out. A series of intermediates and a binuclear palladium(II) complex could be characterized by X-ray crystal structure analysis

  首次在1,1'-联萘骨架上实现了二苯基磷和三唑基单元的结合。这种新型的P,N-配体可以在几个步骤内制备为对映纯化合物。已进行了与二价钯氯化物的配位化学的初步实验。通过X射线晶体结构分析，已确定了一系列中间体和双核二价钯配合物。
• Chiral Sterically Congested Phosphane-Amide Bifunctional Organocatalysts in Asymmetric Aza-Morita–Baylis–Hillman Reactions ofN-Sulfonated Imines with Methyl and Ethyl Vinyl Ketones
  作者：Xiao-Yang Guan、Ying-Qing Jiang、Min Shi

  DOI：10.1002/ejoc.200800050

  日期：2008.4

  series of chiral sterically congested phosphane-amide bifunctional Lewis bases L1-L3 have been successfully synthesized and their application in asymmetric aza-Morita-Baylis-Hillman (aza-MBH) reactions of N-sulfonated imines with activated olefins such as methyl and ethyl vinyl ketone has been investigated under mild conditions. The corresponding aza-MBH adducts can be obtained in good-to-excellent yields

  一系列手性空间拥挤的磷酰胺双功能路易斯碱L1-L3已成功合成并在N-磺化亚胺与甲基和乙基等活化烯烃的不对称氮杂-森田-贝利斯-希尔曼（aza-MBH）反应中的应用乙烯基酮已在温和条件下进行了研究。相应的 aza-MBH 加合物可以在室温（20 摄氏度）的二氯甲烷中以良好到优异的产率（高达 98%）和中等至良好的对映选择性（高达 91 或 93% ee）获得。新型手性双功能磷烷路易斯碱。((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)。
• 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。