N,N'-bis[(S)-N-benzyloxycarbonylprolyl]-1,2-ethylenediamine

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N,N'-bis[(S)-N-benzyloxycarbonylprolyl]-1,2-ethylenediamine
• 英文别名: N,N'-bis[(S)-N-benzyloxycarbonylprolyl]ethylenediamine；N,N'-bis(carbobenzoxy-S-prolyl)-1,2-ethanediamine；Z-ProNH(CH2)2NHPro-Z；N,N'-Bis-(N-carbobenzoxy-S-prolyl)-ethylendiamin；N,N'-bis(N-Cbz-L-proline)-1,2-diaminoethane；benzyl (2S)-2-[2-[[(2S)-1-phenylmethoxycarbonylpyrrolidine-2-carbonyl]amino]ethylcarbamoyl]pyrrolidine-1-carboxylate
• 化学式: C₂₈H₃₄N₄O₆
• 分子量: 522.601
• InChiKey: POWPRIXONCWILX-ZEQRLZLVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  38
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  117
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  N,N'-bis[(S)-N-benzyloxycarbonylprolyl]-1,2-ethylenediamine 在 palladium on activated charcoal lithium aluminium tetrahydride 、 环己烯 作用下， 以 四氢呋喃 为溶剂， 反应 25.0h， 生成 N,N'-双[[(2S)-吡咯烷-2-基]甲基]乙烷-1,2-二胺
  参考文献：
  名称：

  Rh and Ir complexes containing multidentate, C2-symmetry ligands. Structural and catalytic properties in asymmetric hydrogenation

  摘要：

  A comparative investigation of the interaction of Rh(I) and Ir(I) with a series of mixed-donor multidentate, C-2-symmetry ligands has been carried out. The complexes have been prepared by the reaction of [MCl(cod)](2) (cod = 1,5-cyclooctadiene) with AgPF6 and further treatment with the ligand. All ligands form 1:1 (metal:ligand) species with the above metal ions although, in a few instances, species of type [M2L2](2+) were also detected. The structures of these complexes were elucidated by analytical and spectroscopic data (elemental analysis, mass spectroscopy, IR, H-1- and C-13-NMR). Complexes were tested in the asymmetric hydrogenation of prochiral olefins, providing enantioselectivities up to 36%. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00083-8
• 作为产物：
  描述：

  N-苄氧羰基-L-脯氨酸 在 二苯基磷酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 生成 N,N'-bis[(S)-N-benzyloxycarbonylprolyl]-1,2-ethylenediamine
  参考文献：
  名称：

  核心修饰的双脯氨酸肽自组装成无限氢键 β-折叠带的一个独特例子：Z-ProNH(CH2)2NHPro-Z 的晶体结构

  摘要：

  Z-ProNH(CH2)2NHPro-Z 的晶体结构表现出延伸的主链，在两个脯氨酰残基之前同时出现顺式和反式构象，自组装成无限氢键 β-折叠带。

  DOI：

  10.1039/b009532j

文献信息

• Nickel(ii) complexes with amide ligands: oxidative dehydrogenation of the amines in a tetradentate diamide–diamine ligand
  作者：Colin L. Weeks、Peter Turner、Ronald R. Fenton、Peter A. Lay

  DOI：10.1039/b107378h

  日期：——

  Four complexes were prepared by the reaction of Ni(II) with three pyrrolidine based diamide–diamine ligands. The two amine groups in the ligand N,N′-bis(S-prolyl)-1,2-ethanediamine (S,S-bprolenH2) were oxidatively dehydrogenated during the preparation of the Ni(II) complex in air. The reaction involved O2 to yield a complex of a tetradentate ligand with 1-pyrroline terminal groups. The Ni(II) complex with S,S-bprolenH2 was synthesised under oxygen-free conditions, and the Ni(II) complexes with the analogous ligands N,N′-bis(S-prolyl)-R,R-1,2-cyclohexanediamine (R,R-(S,S)-bprolchxnH2) and N,N′-bis(S-prolyl)-1,2-benzenediamine (S,S-bprolbenH2) were prepared in air. The complexes were characterised by X-ray crystallography, 1H and 13C NMR spectroscopy and IR spectroscopy. The Ni(III/II) reduction potentials of complexes with pyridyl and pyrrolidine based tetradentate diamide ligands were measured by cyclic voltammetry to assess the stability of the Ni(III) oxidation state, but did not show any correlation with the ease of ligand oxidation.

  通过Ni(II)与三种以吡咯烷为基础的二胺–二酰胺配体的反应，制备了四个配合物。在配体N,N'-双(S-丙氨基)-1,2-乙二胺(S,S-bprolenH2)的制备过程中，两个胺基在空气中被氧化脱氢。该反应涉及O2，生成一种具有1-吡咯啉末端基团的四齿配体的配合物。在无氧条件下合成了与S,S-bprolenH2的Ni(II)配合物，而与类似配体N,N'-双(S-丙氨基)-R,R-1,2-环己烷二胺(R,R-(S,S)-bprolchxnH2)及N,N'-双(S-丙氨基)-1,2-苯二胺(S,S-bprolbenH2)的Ni(II)配合物则是在空气中制备的。这些配合物通过X射线晶体学、1H和13C NMR光谱以及红外光谱进行表征。采用循环伏安法测定了与以吡啶和吡咯烷为基础的四齿二酰胺配体的配合物的Ni(III/II)还原电位，以评估Ni(III)氧化态的稳定性，但未表现出与配体氧化难易程度的相关性。
• Copper(ii) complexes of bis(amino amide) ligands: effect of changes in the amino acid residue
  作者：Inés Martí、Armando Ferrer、Jorge Escorihuela、M. Isabel Burguete、Santiago V. Luis

  DOI：10.1039/c2dt12459a

  日期：——

  A family of ligands derived from bis(amino amides) containing aliphatic spacers has been prepared, and their protonation and stability constants for the formation of Cu2+ complexes have been determined potentiometrically. Important differences are associated to both the length of the aliphatic spacer and the nature of the side chains derived from the amino acid. In general, ligands containing aliphatic

  已经制备了衍生自含脂肪族间隔基的双（氨基酰胺）的配体族，并且已经用电位法确定了其形成Cu 2+配合物的质子化和稳定性常数。重要的差异与脂族间隔基的长度和衍生自氨基酸的侧链的性质有关。通常，含脂族侧链的配体显示出较高的碱度以及对Cu 2+的稳定性常数。同样，当降低由相应侧链引起的位阻时，碱度和稳定性常数趋于增加。FT-IR，UV-vis和ESI-MS用于分析形态图中检测到的复杂物种。UV-vis研究表明铜（II）配合物存在不同的配位环境。在某些情况下可以形成具有不同化学计量的配合物。ESI-MS实验清楚地突出了这一点。
• <i>C</i>₂-Symmetric Bisprolinamide as a Highly Efficient Catalyst for Direct Aldol Reaction
  作者：Sampak Samanta、Jinyun Liu、Rajasekhar Dodda、Cong-Gui Zhao

  DOI：10.1021/ol052277f

  日期：2005.11.1

  [reaction: see text] The catalytic activity of the prolinamide-type catalysts may be improved by introducing additional prolinamide moiety into the catalyst, while the enantioselectivity can still be maintained or further improved. A C2-symmetric bisprolinamide with two prolinamide moieties has been found to be an excellent catalyst for direct aldol reaction with more than doubled reactivity and better

  [反应：见正文]可以通过将另外的脯氨酰胺部分引入到催化剂中来改善脯氨酰胺型催化剂的催化活性，同时仍然可以保持或进一步提高对映选择性。已经发现具有两个脯氨酰胺部分的C 2对称双脯氨酰胺是直接羟醛反应的极好催化剂，其反应性比单脯氨酰胺对应物高一倍以上，并且不对称诱导性更好。
• A hybrid cyclic bisproline designed to adopt a β-fold: crystal structure of cyclo(ProNHCH2CH2NHProCOCH2CH2CO)
  作者：Darshan Ranganathan、M. Gopi Kumar、Isabella L. Karle

  DOI：10.1039/b009130h

  日期：——

  The crystal structure of 14-membered cyclo(ProNHCH2CH2NHProCOCH2CH2 CO) reveals the presence of an internal NH⋯OC bond dividing the molecule into two halves of 10-membered hydrogen-bonded rings; the molecules self-assemble into cyclic dimers through a symmetrical pair of intermolecular NH⋯OC hydrogen bonds; a layered structure is formed, alternating layers of cyclic dimers and layers of chloroform molecules, all of which make strong CH⋯O hydrogen bonds with the cyclic dimers.

  14 元环(ProNHCH2CH2NHProCOCH2CH2 CO)的晶体结构显示，分子内部存在一个 NHâ¯OC 键，将分子分为两半 10 元氢键环； 分子通过一对对称的分子间 NHâ¯OC 氢键自组装成环状二聚体；形成层状结构，环状二聚体层和氯仿分子层交替出现，所有氯仿分子都与环状二聚体形成牢固的 CHâ¯O 氢键。
• Rh and Ir complexes containing multidentate, C2-symmetry ligands. Structural and catalytic properties in asymmetric hydrogenation
  作者：M.J Alcón、M Iglesias*、F Sánchez*、I Viani

  DOI：10.1016/s0022-328x(00)00083-8

  日期：2000.4

  A comparative investigation of the interaction of Rh(I) and Ir(I) with a series of mixed-donor multidentate, C-2-symmetry ligands has been carried out. The complexes have been prepared by the reaction of [MCl(cod)](2) (cod = 1,5-cyclooctadiene) with AgPF6 and further treatment with the ligand. All ligands form 1:1 (metal:ligand) species with the above metal ions although, in a few instances, species of type [M2L2](2+) were also detected. The structures of these complexes were elucidated by analytical and spectroscopic data (elemental analysis, mass spectroscopy, IR, H-1- and C-13-NMR). Complexes were tested in the asymmetric hydrogenation of prochiral olefins, providing enantioselectivities up to 36%. (C) 2000 Elsevier Science S.A. All rights reserved.