N,N'-Bis-(S-prolyl)-ethylendiamin | 54985-58-9

• 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-prolyl)-ethylendiamin
• 英文别名: (2S)-N-[2-[[(2S)-pyrrolidine-2-carbonyl]amino]ethyl]pyrrolidine-2-carboxamide
• CAS: 54985-58-9
• 化学式: C₁₂H₂₂N₄O₂
• 分子量: 254.332
• InChiKey: ZLULQGQKUNFCBL-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  82.3
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N,N'-Bis-(S-prolyl)-ethylendiamin 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以70%的产率得到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 N-羟基琥珀酰亚胺酯 在 氢溴酸 作用下， 以 乙二醇二甲醚 、 溶剂黄146 为溶剂， 反应 15.0h， 生成 N,N'-Bis-(S-prolyl)-ethylendiamin
  参考文献：
  名称：

  双（氨基酰胺）配体的 铜（ii）配合物：氨基酸残基变化的影响†

  摘要：

  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。

  DOI：

  10.1039/c2dt12459a

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。
• Enantioselective Cyanosilylation of Ketones Catalyzed by a Nitrogen-Containing Bifunctional Catalyst
  作者：Yan Xiong、Xiao Huang、Shaohua Gou、Jinglun Huang、Yuehong Wen、Xiaoming Feng

  DOI：10.1002/adsc.200505418

  日期：2006.3

  An efficient and optically active, bifunctional tetraaza ligand (2S)-N-(1R,2R)-2-[(S)-pyrrolidine-2-carboxamido]-1,2-diphenylethyl}pyrrolidine-2-carboxamide has been developed for the addition of trimethylsilyl cyanide (TMSCN) to ketones. The bifunctional catalyst system based on a monometallic titanium complex was found to be a highly enantioselective catalyst to provide O-TMS cyanohydrins with up

  一种高效且旋光的双官能四氮杂配体（2 S）-N -（1 R，2 R）-2-[（S）-吡咯烷-2-甲酰胺基] -1,2-二苯乙基}吡咯烷-2-甲酰胺已经开发出将三甲基甲硅烷基氰化物（TMSCN）添加到酮中的方法。发现基于单金属钛配合物的双官能催化剂体系是高度对映选择性的催化剂，其提供高达94％ee的O -TMS氰醇。已经提出了一种可能的过渡态来解释激活和不对称电感的起源。
• Ring-closing metathesis approach for the synthesis of optically active l-proline-based macrocycles
  作者：Talal F. Al-Azemi、Abdirahman A. Mohamod、Mickey Vinodh

  DOI：10.1016/j.tet.2015.01.041

  日期：2015.3

  applications in supramolecular chemistry, such as in chiral discrimination and chiral catalysis. In this study, the synthesis of novel optically active macrocyclic compounds based on l-proline is reported. The key step in the synthetic strategy is the utility of a ring-closing metathesis (RCM) technique. The synthesized macrocyclic compounds have been characterized by NMR, mass analysis, and single crystal

  手性大环化合物在超分子化学中发现了许多有趣的应用，例如在手性鉴别和手性催化中。在该研究中，报道了基于1-脯氨酸的新型旋光性大环化合物的合成。合成策略中的关键步骤是闭环复分解（RCM）技术的实用性。合成的大环化合物已通过NMR，质量分析和单晶X射线晶体学进行了表征。以（rac）-扁桃酸（2-羟基-2-苯基乙酸）为模型实例证明了这些大环化合物作为对映体鉴别剂的应用。
• <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。