(R)-N-(1-(p-tolyl)ethyl)-P,P-diphenylphosphinic amide

• 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)-N-(1-(p-tolyl)ethyl)-P,P-diphenylphosphinic amide
• 英文别名: N-[1-(4-methylphenyl)ethyl]-P,P-diphenylphosphinoylamide；(R)-N-[1-(4-methylphenyl)ethyl]-P,P-diphenylphosphinoylamide；(1R)-N-diphenylphosphoryl-1-(4-methylphenyl)ethanamine
• 化学式: C₂₁H₂₂NOP
• 分子量: 335.386
• InChiKey: TVNUHJHYMDNSRE-GOSISDBHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  乙酰氯 、 (R)-N-(1-(p-tolyl)ethyl)-P,P-diphenylphosphinic amide 在 4-二甲氨基吡啶 、 水 作用下， 反应 0.5h， 生成 (R)-N-[1-(4-methylphenyl)ethyl]acetamide
  参考文献：
  名称：

  Reaction prospecting by 31P NMR: enantioselective rhodium-DuPhos catalysed addition of ZnMe2 to diphenylphosphinoylimines

  摘要：

  Chiral shift P-31 NMR spectroscopy allows the identification of ligand leads in asymmetric catalyst systems for ZnMe2 addition to ArCH=NP(C)Ph-2. Subsequent GC-based optimisation shows [RhC](CH2=CH2)(2)](2) and (RR)-MeDuPhos to be the optimal pre-catalyst combination (product in 78-93% ee). Transmetallation of [(MeDuPhos)Rh{N(P(O)Ph-2-CHMeAr}] with ZnMe2 appears to be the rate limiting step of the catalytic cycle as competing coordination by the imine starting material leads to Ph2P(O)NHCH2Ar via MVP hydrogen-transfer. This limitation can largely be overcome by the slow addition of the imine. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.09.020
• 作为产物：
  描述：

  N-[(1E)-1-(4-methylphenyl)ethylidene]-P,P-diphenylphosphinic amide 在 di(norbornadiene)rhodium(I) tetrafluoroborate (R)-⁽¹⁾-{[(S)-2-((cHx)2phosphino)ferrocenyl]ethyl}P(cHx)2 、 氢气 作用下， 以 甲醇 为溶剂， 60.0 ℃ 、7.0 MPa 条件下， 反应 21.0h， 生成 (R)-N-(1-(p-tolyl)ethyl)-P,P-diphenylphosphinic amide
  参考文献：
  名称：

  The Highly Enantioselective Hydrogenation ofN-Diphenylphosphinylketimines with Cationic Rh Ferrocenyldiphosphine Catalysts

  摘要：

  DOI：

  10.1002/1615-4169(20010129)343:1<68::aid-adsc68>3.0.co;2-g

文献信息

• Synthesis of Air- and Moisture-Stable, Storable Chiral Oxorhenium Complexes and Their Application as Catalysts for the Enantioselective Imine Reduction
  作者：Braja Gopal Das、Rajender Nallagonda、Dhananjay Dey、Prasanta Ghorai

  DOI：10.1002/chem.201501914

  日期：2015.9.1

  salicyloxazoline based oxorhenium(V) complexes have been synthesized and their catalytic application for the asymmetric reduction of ketimines using hydrosilane as hydride source is disclosed. A broad substrate scope, high yields, and excellent enantioselectivities (up to 99 %) are attained. Furthermore, the syntheses of enantiopure α‐amino esters, γ‐ and δ‐lactams, and isoindolinones have also been carried

  合成了空气/水分稳定，晶体和可储存的手性水杨基恶唑啉基氧化（V）配合物，并公开了其在氢化硅烷作为氢化物源的情况下催化不对称还原酮亚胺的催化应用。获得了广泛的底物范围，高收率和出色的对映选择性（最高99％）。此外，对映体纯α-氨基酯，γ-和δ-内酰胺以及异吲哚啉酮的合成也已使用该方法进行。最后，该方法已应用于具有药物相关性的合成靶标，例如R -（+）-沙丁胺碱和R -（+）-crispine A.
• Asymmetric Transfer Hydrogenation of Ketimines Using Well-Defined Iron(II)-Based Precatalysts Containing a PNNP Ligand
  作者：Alexandre A. Mikhailine、Mazharul I. Maishan、Robert H. Morris

  DOI：10.1021/ol302079q

  日期：2012.9.7

  complexes containing PNNP ligands catalyze a highly enantioselective reduction of N-(diphenylphosphinoyl)- and N-(p-tolylsulphonyl)-ketimines. Under mild conditions and low catalyst loading, the ketimines are successfully reduced to the corresponding amines in enantiomeric excess ranging from 94 to 99%.

  含PNNP配体的明确定义的铁（II）基络合物催化N-（二苯基膦酰基）-和N-（对甲苯磺酰基）-酮亚胺的高度对映选择性还原。在温和的条件下和低的催化剂负载量下，酮亚胺成功地以94至99％的对映体过量还原为相应的胺。
• METHOD OF ENANTIOSELECTIVE ADDITION TO IMINES
  申请人：UANG Biing-Jiun

  公开号：US20120004441A1

  公开（公告）日：2012-01-05

  The present invention relates to a method of enantioselective addition to imines, including: reacting R 3 CH═NY with R 4 ZnR 5 in the presence of a compound represented by the following formula (I), in which Y, R 1 , R 2 , R 3 , R 4 and R 5 are defined the same as the specification. Accordingly, the present invention can prepare secondary amines in high yields and enantiomeric excess by the above-mentioned method.

  本发明涉及一种对亚胺进行对映选择性加成的方法，包括：在以下式(I)所代表的化合物存在下，将R3CH═NY与R4ZnR5反应，其中Y、R1、R2、R3、R4和R5的定义与规范相同。因此，本发明可以通过上述方法高产率和对映过量地制备二级胺。
• Enantioselective Addition of Dialkylzinc to Aromatic Aldimines Mediated by Camphor-Derived Chiral β-Amino Alcohols
  作者：Wei-Ming Huang、Biing-Jiun Uang

  DOI：10.1002/asia.201403240

  日期：2015.4

  The enantioselective addition of diethylzinc or dimethylzinc to N‐(diphenylphosphinoyl)imines mediated by 1 or 2 could be achieved in high yields (70–97 %) and enantioselectivities (85–98 % ee). The catalytic loading of 1 or 2 a could be reduced to 10 mol % for methylation or ethylation of imines in high yields and enantioselectivities (79–96 %) when the reaction was conducted in the presence of 1

  在1或2介导的N-（二苯基膦酰基）亚胺中对二乙基锌或二甲基锌的对映选择性加成（70-97％）和对映选择性（85-98％ee）可以实现。当反应在1.8当量甲醇的存在下进行时，亚胺的甲基化或乙基化反应可以将1或2 a的催化负载降低至10 mol％，从而获得高收率和对映选择性（79-96％）。ñ单取代的氨基醇比他们更高的诱导对映选择性ñ，ñ在我们的催化体系双取代同类。
• Enantioselective Synthesis of Amines: General, Efficient Iron-Catalyzed Asymmetric Transfer Hydrogenation of Imines
  作者：Shaolin Zhou、Steffen Fleischer、Kathrin Junge、Shoubhik Das、Daniele Addis、Matthias Beller

  DOI：10.1002/anie.201002456

  日期：2010.10.25

  A readily accessible, active iron catalyst serves in the straightforward, catalytic transfer hydrogenation of imines (see scheme). A series of imines are converted into chiral amines in high yields and very good enantioselectivities. This method should find broad application in the search for bioactive chiral amines.

  在铁器时代：一种易于获得的活性铁催化剂可用于亚胺的直接催化转移加氢（参见方案）。一系列亚胺以高收率和非常好的对映选择性被转化为手性胺。该方法应在寻找生物活性手性胺中找到广泛的应用。