(S)-N-[1-(2-methoxyphenyl)propyl]-P,P-diphenylphosphinoylamide | 638132-68-0

• 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: (S)-N-[1-(2-methoxyphenyl)propyl]-P,P-diphenylphosphinoylamide
• 英文别名: N-[1-(2-methoxyphenyl)propyl]-P,P-diphenylphosphinoylamide；N-[(1S)-1-(2-Methoxyphenyl)propyl]-P,P-diphenylphosphinic amide；(1S)-N-diphenylphosphoryl-1-(2-methoxyphenyl)propan-1-amine
• CAS: 638132-68-0
• 化学式: C₂₂H₂₄NO₂P
• 分子量: 365.412
• InChiKey: PJPWOQOCIHOSPX-NRFANRHFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  diethylzinc 、 (E)-N-(2-methoxybenzylidene)-P,P-diphenylphosphinic amide 在 copper(II) bis(trifluoromethanesulfonate) 、 1,2-双[(2R,5R)-2,5-二甲基磷]一氧化苯 作用下， 以 甲苯 为溶剂， 反应 20.5h， 生成 (R)-N-[1-(2-methoxyphenyl)propyl]-P,P-diphenylphosphinoylamide 、 (S)-N-[1-(2-methoxyphenyl)propyl]-P,P-diphenylphosphinoylamide
  参考文献：
  名称：

  使用新型双（膦）一氧化物手性配体不对称催化合成 α-手性胺

  摘要：

  我们已经证明 Me-DuPHOS 一氧化 (BozPHOS) 在铜催化下将二烷基锌加成到 N-膦亚胺中是一种非常有效的配体，提供了获得 α-手性胺的途径。新配体对于添加反应性较低的二甲基锌特别有效。该方法的主要优点是收率高、底物范围广、对映选择性高、催化剂负载量低（3 mol%）。

  DOI：

  10.1021/ja038291+

文献信息

• Asymmetric, Catalytic Synthesis of α-Chiral Amines Using a Novel Bis(phosphine) Monoxide Chiral Ligand
  作者：Alessandro A. Boezio、Julien Pytkowicz、Alexandre Côté、André B. Charette

  DOI：10.1021/ja038291+

  日期：2003.11.1

  We have shown that Me-DuPHOS monoxide (BozPHOS) is a very effective ligand in the copper-catalyzed addition of dialkylzinc to N-phosphinoylimines providing access to alpha-chiral amines. The new ligand is particularly effective for the addition of the lesser reactive dimethylzinc. The major advantages of this process are high yields, broad substrate scope, and high enantioselectivities with low catalyst

  我们已经证明 Me-DuPHOS 一氧化 (BozPHOS) 在铜催化下将二烷基锌加成到 N-膦亚胺中是一种非常有效的配体，提供了获得 α-手性胺的途径。新配体对于添加反应性较低的二甲基锌特别有效。该方法的主要优点是收率高、底物范围广、对映选择性高、催化剂负载量低（3 mol%）。
• 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。
• Novel chiral copper complexes of N,P-ferrocenyl ligands with central and planar chirality as efficient catalyst for asymmetric addition of diethylzinc to imines
  作者：Min-Can Wang、Lan-Tao Liu、Yuan-Zhao Hua、Jun-Song Zhang、Yan-Yan Shi、De-Kun Wang

  DOI：10.1016/j.tetasy.2005.06.005

  日期：2005.8

  A new type of chiral copper complexes of N,P-ferrocenyl ligands with central and planar chirality as efficient catalyst was applied to the enantioselective addition of diethylzinc to N-diphenylphosphinoylimines. The (R)- and (s)-enantiomers of the addition reaction were obtained for this transformation. In the presence of 6 mol % of bidentate ligand 1 and 12 mol % of Cu(OTf)(2), the asymmetric addition process affords N-diphenylphosphinoylamides in up to 97% ee and 95% yields. (c) 2005 Elsevier Ltd. All rights reserved.
• Chiral ferrocenyl amidophosphine ligand for highly enantioselective addition of diethylzinc to N-diphenylphosphinoylimines
  作者：Min-Can Wang、Cui-Lian Xu、Fu Cheng、Xue Ding

  DOI：10.1016/j.tet.2006.10.015

  日期：2006.12

  The asymmetric addition of diethylzine to N-diphenylphosphinoylimines afforded N-diphenylphosphinoylamides with enantioselectivity of up to 90% ee in the presence of a catalytic amount of chiral ligand (S)-N-ferrocenoyl-2-[(diphenylphosphino)methyll-pyrrolidine 13 (7 mol %) and Cu(OTf)(2) (15 mol %). The remarkable improvement of enantioselectivities, as compared with the same type of chiral ligand 6, could be explained by the unique structure of ferrocenyl amidophosphine ligand combining with the reactive intermediate of this addition reaction. (c) 2006 Elsevier Ltd. All rights reserved.
• Synthesis of novel well-defined chain-end-functionalized polystyrenes with dendritic chiral ephedrine moieties and their applications as highly enantioselective diethylzinc addition to N-diphenylphosphinoyl arylimines
  作者：Ashraf A. El-Shehawy

  DOI：10.1016/j.tet.2007.08.093

  日期：2007.11

  A series of novel well-defined chain-end-functionalized polystyrenes having 2, 4, 8, and 16 chiral ephedrine moieties dendritically distributed at their hyperbranched chain-ends were quantitatively synthesized. Their well-defined architectures were fully confirmed by elemental analysis, FTIR, SEC as well as by 1H and 13C NMR spectroscopies. These polymers were precisely controlled in the molecular

  定量合成了一系列新颖的，定义明确的，具有2、4、8和16个手性麻黄碱部分在其超支化链端分布的手性麻油碱部分的链端官能化聚苯乙烯。通过元素分析，FTIR，SEC以及1 H和13 C NMR光谱学充分证实了它们的明确定义的体系结构。这些聚合物的分子量和分子量分布均得到精确控制，链端官能团也得到了明确定义。这些树状手性聚合物在二乙基锌向一系列N的对映选择性加成中充当高度对映选择性的手性配体-二苯基膦酰基芳基丙氨酸。其中，在链末端具有八个麻黄碱部分的手性树枝状聚合物以高至高收率提供了对映异构体富集的膦酰基酰胺，其对映选择性高达93％ee。所获得的对映选择性与使用N-苄基麻黄碱及其相应的共聚物作为手性配体所获得的对映选择性相当。