(R)-(-)-2-amino-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-amino-2'-diphenylphosphinyl-1,1'-binaphthyl
• 英文别名: (R)-2'-(diphenylphosphinoyl)-[1,1']binaphthalenyl-2-yl-amine；1-(2-(diphenylphosphino)naphthalen-1-yl)naphthalen-2-amine；1-(2-Diphenylphosphorylnaphthalen-1-yl)naphthalen-2-amine
• 化学式: C₃₂H₂₄NOP
• 分子量: 469.522
• InChiKey: VUYJRFQJPRJZNE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  35
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  43.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-(-)-2-amino-2'-diphenylphosphinyl-1,1'-binaphthyl 在 sodium iodide 三氯硅烷 、 碳酸氢钠 、 N,N-二甲基苯胺 作用下， 以 甲苯 、 均三甲苯 为溶剂， 生成 (3S,4S)-1-(2'-Diphenylphosphanyl-[1,1']binaphthalenyl-2-yl)-3,4-dimethoxy-pyrrolidine
  参考文献：
  名称：

  The synthesis of a new generation of MAP ligands containing two types of chiral elements for asymmetric catalysis

  摘要：

  A series of novel aminophosphine ligands containing both axial and central chirality have been synthesized for the first time from NOBIN and tartaric acid derivatives. Their capability for asymmetric induction in the Pd-catalyzed reaction of 1,3-diphenylprop-2-en-1-yl acetate and dimethyl malonate was investigated and the results clearly demonstrated that correct assembly of axial chirality in the scaffold and central chirality of the modification group was very important for achieving higher enantioselectivity in the reaction. In a matched case, the asymmetric allylation product could be obtained in 85.6% ec. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)02056-1
• 作为产物：
  描述：

  diphenylphosphine oxide 在 氢氧化钾 、 sodium hydroxide 、 三氟甲磺酸酐 、 双氧水 、 溴 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 25.25h， 生成 (R)-(-)-2-amino-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

• 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。
• 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。
• Cooperativity in the counterion catalysis of Morita/Baylis/Hillman reactions promoted by enantioselective trifunctional organocatalysts
  作者：Christopher Anstiss、Fei Liu

  DOI：10.1016/j.tet.2010.05.007

  日期：2010.7

  New trifunctional organocatalysts with a NHTs Brønsted acid were prepared and tested in their ability to promote the counterion catalysis of generic and aza-Morita/Baylis/Hillman reactions. The cooperativity between the counterion and the NHTs Brønsted acid of the trifunctional catalyst was required for good enantioselectivity and rate enhancement. Better enantioselectivity was observed for aza-MBH

  制备了具有NHTs布朗斯台德酸的新型三官能有机催化剂，并测试了它们促进普通反应和aza-Morita / Baylis / Hillman反应的抗衡离子催化能力。为了良好的对映选择性和速率提高，需要三官能催化剂的抗衡离子与NHTs布朗斯台德酸之间的协同作用。在较容易的条件下，在相对较低的催化剂负载量（2–5 mol％）下，氮杂-MBH反应观察到更好的对映选择性。
• 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)。
• Asymmetric catalytic aza-Morita–Baylis–Hillman reaction using chiral bifunctional phosphine amides as catalysts
  作者：Ming-Juan Qi、Teng Ai、Min Shi、Guigen Li

  DOI：10.1016/j.tet.2007.11.039

  日期：2008.2

  The asymmetric catalytic aza-Morita–Baylis–Hillman reaction of N-sulfonated imines with α,β-unsaturated ketones has been successfully conducted by using chiral bifunctional phosphine amides as catalysts. A series of new chiral bifunctional phosphine amides were designed, synthesized, and systematically studied for this asymmetric reaction. The corresponding aza-MBH adducts were obtained in good yields

  N-磺化亚胺与α，β-不饱和酮的不对称催化氮杂-Morita-Baylis-Hillman反应已通过使用手性双官能膦酰胺作为催化剂成功进行。针对该不对称反应，设计，合成和系统地研究了一系列新的手性双官能膦酰胺。在温和的条件下，获得的相应氮杂-MBH加合物收率良好（75–99％），对映体过量非常好（51–95％ee）。