N,N'-bis{[(S)-pyrrolidin-2-yl]methyl}-1,2-phenylenediamine | 384333-95-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N,N'-bis{[(S)-pyrrolidin-2-yl]methyl}-1,2-phenylenediamine
• 英文别名: N,N'-bis([(S)-pyrrolidin-2-yl]methyl)phenylenediamine；N,N'-bis{[(S)-pyrrolidin-2-yl]methyl}phenylenediamine；N,N'-bis[N-benzyl-(S)-prolyl]phenylenediamine；1-N,2-N-bis[[(2S)-pyrrolidin-2-yl]methyl]benzene-1,2-diamine
• CAS: 384333-95-3
• 化学式: C₁₆H₂₆N₄
• 分子量: 274.409
• InChiKey: AXTWMQOSPRJVJY-KBPBESRZSA-N

物化性质

• 沸点：
  461.6±15.0 °C(Predicted)
• 密度：
  1.098±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  48.1
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tetrakis(acetonitrile)copper(I) perchlorate 、 水 、 N,N'-bis{[(S)-pyrrolidin-2-yl]methyl}-1,2-phenylenediamine 以 乙腈 为溶剂， 以70%的产率得到[Cu(N,N'-bis(N-benzyl-(S)-prolyl)phenylenediamine)](ClO4)*2H2O
  参考文献：
  名称：

  Copper and manganese complexes with C2-multitopic ligands. X-ray crystal structure of [Cu(N,N′-bis[(S)-prolyl]phenylenediamine)H2O]. Catalytic properties

  摘要：

  Eight mononuclear complexes with multitopic C-2-symmetry ligands, [Cu(L)]ClO4, [Mn(L)Cl(H2O)]PF6, (L = N,N'-bis[(S)-prolyl]phenylenediamine (1), N,N'-bis[(S)-N-benzylprolyl]phenylenediamine (2), N,N'-bis{[(S)-pyrrolidin-2-yl]methyl}phenylenediamine (3), N,N'-bis-{[(S)-N-benzyl-pyrrolidin-2-yl]methyl}phenylenediamine (4)) have been prepared and characterised by analytical (elemental analysis, and mass spectroscopy) and FT IR, NMR and electronic spectroscopies. The data show that the ligands are neutral and coordinate to the metal in a tetradentate manner. The N,N'-bis[(S)-prolyl]phenylenediamine ligand also appears as an anionic species, (LH-2), and the single crystal structure determination of the respective complex, [Cu(1)]H2O, is reported. This new family of Cu-complexes catalyse the cyclopropanation of styrene with ethyl and t-butyl diazoacetate to afford cis/trans 2-phenylcyclopropan-1-carboxylates with good yields and selectivity against dimerisation and low ee ( < 10%). On the other hand, the manganese and copper complexes also catalyse the oxidation of organic sulfides to sulfoxides with high selectivity, and moderate to low en antioselectivity. If an excess of oxidant were used the reaction yields sulfone as only product with excellent yield. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)00768-5
• 作为产物：
  描述：

  N-苄氧羰基-L-脯氨酸 在 palladium on activated charcoal sodium tetrahydroborate 、 氯甲酸乙酯 、 三乙胺 、 三氟乙酸 、 环己烯 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醇 为溶剂， 反应 51.5h， 生成 N,N'-bis{[(S)-pyrrolidin-2-yl]methyl}-1,2-phenylenediamine
  参考文献：
  名称：

  Synthesis of Rh(I) and Ir(I) complexes with chiral C2-multitopic ligands

  摘要：

  Four multitopic ligands, N,N'-bis[(S)-prolyl)phenylenediamine, N,N'-bis{[(S)-pyrrolidin-2-yl]methyl}phenylenediamine, N,N'-bis[(S)-N-benzylprolyl]phenylenediamine, N,N'-bis{[(S)-N-benzyl-pyrrolidin-2-yl]methyl}phenylenediamine, were synthesised and their co-ordination properties with Rh(I) and Ir(I) studied. The complexes were prepared by the reaction of [MC](cod)](2) with AgPF6 and further treatment with the ligand. All ligands form one to one [ML] species with the above metal ions. The structures of these complexes were elucidated by analytical and spectroscopic data (elemental analysis, mass spectroscopy, IR, H-1- and C-13-NMR). Complexes show excellent activities and enantioselectivities up to 30% for the hydrogenation of prochiral olefins under mild reaction conditions. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(01)01067-1
• 作为试剂：
  描述：

  4-羟基香豆素 、 苄叉丙酮 在 N,N'-bis{[(S)-pyrrolidin-2-yl]methyl}-1,2-phenylenediamine 作用下， 以 氯仿 为溶剂， 生成 (R)-(+)-杀鼠灵 、 (S)-(-)-华法令
  参考文献：
  名称：

  C 2对称的脯氨酸衍生的四胺是高效的催化剂，可直接将不对称的迈克尔酮加成酮加到查耳酮上†

  摘要：

  开发了一种C 2对称四胺催化剂，用于将酮不对称地添加到查耳酮。在温和条件下，以良好的化学收率获得了相应的加合物1,5-二羰基化合物，具有很高的非对映选择性和对映选择性（高达> 99：1 dr和93％ee）。通过研究中间体的ESI-MS，公开了一种提出的机制。

  DOI：

  10.1039/c2ob06897d

文献信息

• C2-symmetric proline-derived tetraamine as highly effective catalyst for direct asymmetric Michael addition of ketones to chalcones
  作者：Shijun Ma、Lulu Wu、Ming Liu、Yongmei Wang

  DOI：10.1039/c2ob06897d

  日期：——

  A C2-symmetric tetraamine catalyst was developed for the asymmetric Michael addition of ketones to chalcones. The corresponding adducts 1,5-dicarbonyl compounds were obtained in good chemical yields with high levels of diastereo- and enantioselectivities (up to >99 : 1 dr and 93% ee) under mild conditions. By studying the ESI-MS of the intermediates, a proposed mechanism was disclosed.

  开发了一种C 2对称四胺催化剂，用于将酮不对称地添加到查耳酮。在温和条件下，以良好的化学收率获得了相应的加合物1,5-二羰基化合物，具有很高的非对映选择性和对映选择性（高达> 99：1 dr和93％ee）。通过研究中间体的ESI-MS，公开了一种提出的机制。
• Synthesis of Rh(I) and Ir(I) complexes with chiral C2-multitopic ligands
  作者：M.J. Alcón、M. Iglesias、F. Sánchez、I. Viani

  DOI：10.1016/s0022-328x(01)01067-1

  日期：2001.9

  Four multitopic ligands, N,N'-bis[(S)-prolyl)phenylenediamine, N,N'-bis[(S)-pyrrolidin-2-yl]methyl}phenylenediamine, N,N'-bis[(S)-N-benzylprolyl]phenylenediamine, N,N'-bis[(S)-N-benzyl-pyrrolidin-2-yl]methyl}phenylenediamine, were synthesised and their co-ordination properties with Rh(I) and Ir(I) studied. The complexes were prepared by the reaction of [MC](cod)](2) with AgPF6 and further treatment with the ligand. All ligands form one to one [ML] species with the above metal ions. The structures of these complexes were elucidated by analytical and spectroscopic data (elemental analysis, mass spectroscopy, IR, H-1- and C-13-NMR). Complexes show excellent activities and enantioselectivities up to 30% for the hydrogenation of prochiral olefins under mild reaction conditions. (C) 2001 Elsevier Science B.V. All rights reserved.
• Copper and manganese complexes with C2-multitopic ligands. X-ray crystal structure of [Cu(N,N′-bis[(S)-prolyl]phenylenediamine)H2O]. Catalytic properties
  作者：M.J Alcón、Marta Iglesias、F Sánchez

  DOI：10.1016/s0020-1693(02)00768-5

  日期：2002.5

  Eight mononuclear complexes with multitopic C-2-symmetry ligands, [Cu(L)]ClO4, [Mn(L)Cl(H2O)]PF6, (L = N,N'-bis[(S)-prolyl]phenylenediamine (1), N,N'-bis[(S)-N-benzylprolyl]phenylenediamine (2), N,N'-bis[(S)-pyrrolidin-2-yl]methyl}phenylenediamine (3), N,N'-bis-[(S)-N-benzyl-pyrrolidin-2-yl]methyl}phenylenediamine (4)) have been prepared and characterised by analytical (elemental analysis, and mass spectroscopy) and FT IR, NMR and electronic spectroscopies. The data show that the ligands are neutral and coordinate to the metal in a tetradentate manner. The N,N'-bis[(S)-prolyl]phenylenediamine ligand also appears as an anionic species, (LH-2), and the single crystal structure determination of the respective complex, [Cu(1)]H2O, is reported. This new family of Cu-complexes catalyse the cyclopropanation of styrene with ethyl and t-butyl diazoacetate to afford cis/trans 2-phenylcyclopropan-1-carboxylates with good yields and selectivity against dimerisation and low ee ( < 10%). On the other hand, the manganese and copper complexes also catalyse the oxidation of organic sulfides to sulfoxides with high selectivity, and moderate to low en antioselectivity. If an excess of oxidant were used the reaction yields sulfone as only product with excellent yield. (C) 2002 Elsevier Science B.V. All rights reserved.