(R)-(-)-N-(1-naphthalen-1-yl-propyl)-P,P-diphenylphosphinic amide | 196521-06-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R)-(-)-N-(1-naphthalen-1-yl-propyl)-P,P-diphenylphosphinic amide
• 英文别名: N-[(1R)-1-(1-naphthyl)propyl]-P,P-diphenylphosphinic amide；N-[1-(1-naphthyl)propyl]-P,P-diphenylphosphinoylamide；(R)-N-[1-(1-Naphthyl)propyl]-P,P-diphenylphosphinamide；Phosphinic amide, N-[(1R)-1-(1-naphthalenyl)propyl]-P,P-diphenyl-；(1R)-N-diphenylphosphoryl-1-naphthalen-1-ylpropan-1-amine
• CAS: 196521-06-9
• 化学式: C₂₅H₂₄NOP
• 分子量: 385.445
• InChiKey: HOWCPYBIVOWFDJ-RUZDIDTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  diethylzinc 、 (E)-N-diphenylphosphoryl-1-naphthalen-1-ylmethanimine 在 (1-benzyl-3-methyl-aziridin-2-yl)-methanol 作用下， 生成 (R)-(-)-N-(1-naphthalen-1-yl-propyl)-P,P-diphenylphosphinic amide 、 N-[(1S)-1-(1-naphthyl)propyl]-P,P-diphenylphosphinic amide
  参考文献：
  名称：

  叠氮基叠氮醇的制备和用作促进二烷基锌试剂与N-（二苯基膦酰基）亚胺对映选择性加成的促进剂。

  摘要：

  已从容易获得的氨基酸（L-丝氨酸，L-苏氨酸和别-L-苏氨酸）或简单烯烃（使用Sharpless不对称氨基羟基化和二羟基化反应）开始合成了一组手性叠氮基醇2-5。已测试手性配体2-5作为促进剂，用于将二烷基锌试剂对映选择性加成到N-（二苯基膦酰基）亚胺1上。研究了取代基对氮丙啶环和醇部分的选择性的影响，并且在最佳条件下在这种情况下，可获得高达94％的对映体过量。最初形成的N-保护的胺6的酸性水解导致相应的游离胺7没有外消旋化。尽管使用了化学计量的配体，大约90％的蛋白质可以在后处理过程中回收并重复使用，而不会造成手性诱导的明显损失。还已经评估了叠氮基叠氮醇2-5作为用于相同反应的催化剂的效用，并且使用0.25当量的手性配体实现了高达76％的对映体过量。还提出了加成反应的可能过渡态。

  DOI：

  10.1021/jo970918h

文献信息

• Catalytic Enantioselective Addition of Dialkylzinc to <i>N</i>-Diphenylphosphinoylimines. A Practical Synthesis of α-Chiral Amines
  作者：Alessandro A. Boezio、André B. Charette

  DOI：10.1021/ja027673x

  日期：2003.2.19

  The enantioselective addition of dialkylzinc reagents to N-diphenylphosphinoylimines derived from aryl-, furyl-, and cyclopropylaldehydes is efficiently catalyzed by a copper(II) triflate/(R,R)-MeDUPHOS complex. The yields are high (51-98%), and the enantiomeric excesses vary from 85 to 96%. This route provides a practical route to alpha-chiral amines.

  二烷基锌试剂与芳基-、呋喃基-和环丙醛衍生的 N-二苯基膦亚胺的对映选择性加成是由三氟甲磺酸铜 (II)/(R,R)-MeDUPHOS 复合物有效催化的。产率高 (51-98%)，对映体过量在 85% 至 96% 之间变化。该路线提供了获得 α-手性胺的实用路线。
• Enantioselective addition of dialkylzincs to N-diphenylphosphinylimines using polymer-supported N,N-dialkylnorephedrines as chiral ligands
  作者：Takefumi Suzuki、Takanori Shibata、Kenso Soai

  DOI：10.1039/a702139i

  日期：——

  Chiral N,N-dialkylnorephedrines supported on polystyrene resin catalyse the enantioselective addition of dialkylzincs to N-diphenylphosphinylimine, affording optically active N-diphenylphosphinylamines with high enantiomeric excess. The influence on the enantioselectivity of the carbon-chain spacer between the chiral function and polymer resin has been examined. Reaction temperature- and solvent-dependency on the chiral polymer-catalysed reaction has also been examined.

  负载于聚苯乙烯树脂上的手性N,N-二烷基去甲肾上腺素催化二烷基锌对手性N-二苯膦亚胺的立体选择性加成反应，生成高对映体过量率的光学活性N-二苯膦亚胺。考察了手性功能团与聚合物树脂之间的碳链间隔对对映选择性的影响。此外，还考察了反应温度和溶剂对这一手性聚合物催化反应的影响。
• Enantioselective Addition of Dialkylzinc Reagents to <i>N</i>-(Diphenylphosphinoyl) Imines Promoted by 2-Azanorbornylmethanols
  作者：David Guijarro、Pedro Pinho、Pher G. Andersson

  DOI：10.1021/jo9718096

  日期：1998.4.1

  the workup. Amino alcohol 2b, that gave the best enantioselectivities in the stoichiometric reaction, was also applied in a catalytic process, and ee's up to 85% were achieved using 0.25 equiv of the ligand, which is the highest ee obtained so far using that catalytic amount of the ligand. Addition products 3 could be converted into the free amines 4 without racemization by acidic hydrolysis. The utility

  已经制备了一组具有2-氮杂降冰片烯骨架的新的β-氨基醇2，并评估了其作为促进二烷基锌试剂向N-（二苯基膦酰基）亚胺1的对映选择性加成的促进剂。 ee最高可达92％。尽管使用了化学计量的配体，但在后处理期间可以回收约90％的配体。在化学计量反应中具有最佳对映选择性的氨基醇2b也用于催化过程，使用0.25当量的配体可达到ee的85％，这是迄今为止使用该催化量的ee获得的最高ee。配体。加成产物3可以不通过酸水解外消旋地转化为游离胺4。
• Asymmetric synthesis of N-diphenylphosphinoylamines by solvent-free enantioselective addition of dialkylzincs to N-diphenylphosphinoylimines
  作者：Itaru Sato、Ryo Kodaka、Kenso Soai

  DOI：10.1039/b106775n

  日期：2001.11.15

  Solvent-free enantioselective addition of dialkylzincs to N-diphenylphosphinoylimines in the presence of chiral 2-morpholino-1-phenylpropan-1-ol affords N-diphenylphosphinoylamines with up to 97% ee. The reaction in the solvent-free system is faster than in organic solvents.

  在手性2-吗啉代-1-苯基丙-1-醇的存在下，无溶剂条件下对N-二苯基膦酰亚胺进行二烷基锌的选择性不对称加成，可以得到最高达97% ee的N-二苯基膦酰胺。与有机溶剂相比，无溶剂体系中的反应速度更快。
• The Catalytic Asymmetric Addition of Diethylzinc toN-(Diphenylphosphinoyl) Imines Catalyzed by Cu(OTf)2-ChiralN-(Binaphthyl-2-yl)thiophosphoramide Ligands
  作者：Min Shi、Chun-Jiang Wang

  DOI：10.1002/adsc.200303041

  日期：2003.8

  Chiral N-(binaphthyl-2-yl)thiophosphoramide L7 [O,O-diethyl 2′-(ethylamino)-1,1′-binaphthyl-2-ylamidothiophosphate] prepared from the reaction of diethyl chlorothiophosphate with (R)-(+)-N-ethyl-1,1′-binaphthyl-2,2′-diamine was used as a catalytic chiral ligand in the first Cu(OTf)2-promoted catalytic asymmetric addition of diethylzinc to N-(diphenylphosphinoyl) imines in which ~85% ee can be realized

  手性ñ - （联萘-2-基）硫代磷酰胺L7 [ O，O-二乙基-2' - （乙基氨基）-1,1'-联萘-2- ylamidothiophosphate]从二氯代硫代磷酸酯与反应制备（[R ）- （+ ）-N-乙基-1,1'-联萘-2,2'-二胺在第一个Cu（OTf）2促进的二乙基锌向N-（二苯基膦酰基）亚胺的催化不对称加成中用作催化手性配体可以实现〜85％ee。