(1R,2R)-N,N′-bis-(isonicotinoyl)-1,2-diphenylethylenediamine | 1562521-00-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮
• 英文名称: (1R,2R)-N,N′-bis-(isonicotinoyl)-1,2-diphenylethylenediamine
• 英文别名: N-[(1R,2R)-1,2-diphenyl-2-(pyridine-4-carbonylamino)ethyl]pyridine-4-carboxamide
• CAS: 1562521-00-9
• 化学式: C₂₆H₂₂N₄O₂
• 分子量: 422.486
• InChiKey: FUFOCBDKDQHADS-DNQXCXABSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  84
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,2R)-N,N′-bis-(isonicotinoyl)-1,2-diphenylethylenediamine 、 (1S,2S)-diphenylethylenediamine zinc(II) bisporphyrin 以 二氯甲烷 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  手性客人手性锌（II）卟啉镊子的络合物：超分子手性的控制，区分和合理化。

  摘要：

  合成了由手性锌（II）双卟啉主体和一系列手性客体组成的一系列1：1夹心复合物，并使主体-客体超分子组装中的手性转移的基础机制合理化。在主持人和来宾中，立体生成中心的数量也各不相同，这使您可以深入了解程序集的整体螺旋度。通过紫外可见光，CD和1研究了手性宿主与手性客人之间的相互作用H NMR光谱滴定以及广泛的DFT研究。有趣的是，具有一个和两个手性中心的手性客人的CD光谱变化非常不同。已经观察到，只有客体具有一个手性中心时，主体-客体复合物的CD偶联的体征是由主体的手性决定的。客体手性的匹配和不匹配只会影响CD信号的幅度；但是，该标志保持不变。形成鲜明对比的是1：1三明治的螺旋度复杂性由拥有两个手性中心的客人的手性决定。但是，当宿主和客体之间的手性匹配时，会观察到CD对的扩增，而错配会导致CD对的反转。对映体宿主也表现出与手性客人相似的趋势，但符号相反。对映体选择性宿主对具有两个手性中心的对

  DOI：

  10.1021/acs.inorgchem.0c00877

文献信息

• Highly Enhanced Bisignate Circular Dichroism of Ferrocene-Bridged Zn(II) Bisporphyrin <i>Tweezer</i> with Extended Chiral Substrates due to Well-Matched Host–Guest System
  作者：Sanfaori Brahma、Sk Asif Ikbal、Avinash Dhamija、Sankar Prasad Rath

  DOI：10.1021/ic401395d

  日期：2014.3.3

  Four new chiral tweezer-diamine complexes, consisting of an achiral ferrocene-bridged Zn(II)bisporhyrin host (1) and two small diamines (1R,2R)-1,2-diphenylethylene diamine (1R,2R)-DPEA} and (1S,2S)-1,2-cyclohexane diamine (1S,2S)-CHDA} and two extended diamines (1R,2R)-N,M-bis-(isonicotinoyl)-1,2-diphenylethylene diamine (1R,2R)-DPEApy} and (1S,2S)-N,N'-bis-(isonicotinoy1)-1,2-cyclohexane diamine (1S,2S)-CHDApy} chiral guests, are reported. Additions of (1R,2R)-DPEA and (1S,2S)-CHDA separately to 1 in dichloromethane result in the formation of 1:1 sandwich complexes 1.DPEA((R,R)) and 1.CHDA((S,S)), respectively, at low guest concentration and 1:2 anti complexes 1.(DPEA((R,R)))(2) and 1.(CHDA((S,S)))(2), respectively, at higher guest concentration. In contrast, separate additions of (1R,2R)-DPEApy and (1S,2S)-CHDApy to I produce only 1:1 sandwich complexes of 1.DPEApy((R,R)) and 1.CHDApy((S,S)) respectively. The binding constants at 295 K between 1 and (1R,2R)-DPEA are observed to be (4.7 +/- 0.2) x 10(4) M-1 and (4.3 +/- 0.3) x 10(3) M-1 for 1:1 sandwich and 1:2 anti form, respectively, while the respective values with (1S,2S)-CHDA are (1.5 +/- 0.2) x 10(5) M-1 and (5.9 +/- 0.3) X 10(3) M-1. However, much larger values of (2.5 +/- 0.3) X 10(5) M-1 and (1.3 +/- 0.3) x 10(6) M-1 have been observed with DPEApy(R,R) and CHDApy((S,S,)), respectively, to produce the corresponding 1:1 sandwich complexes. 1.DPEApy((R,R)) (A(cav) -1759 cm(-1) M-1) (A(cal) = Delta epsilon(1) - Delta epsilon(2), representing the total amplitude of the calculated circular dichroism (CD) couplets) shows similar to 10-fold increase in CD amplitude compared to the values observed for 1.DPEA((R,R)) (A(cal) +187 cm(-1) M-1), while 1.CHDA((S,S)) (A(cal) +1886 cm(-1) M-1), shows nearly 3-fold increase of the CD amplitude compared to the value observed for 1.CHDA((S,S)) (A(cal), -785 cm(-1) M-1) at 295 K. The A(cal) values of -1759 cm(-1) M-1 and +1886 cm(-1) M-1 observed for the 1.DPEApy((R,R)) and 1.CHDApy((S,S)), respectively, are extremely high. To the best of our knowledge, these are some of the largest values reported for a chirality induction process involving bisporphyrin tweezer receptors. The large enhancement in the CD signal intensity is due to the well complementarity size between Zn(11)bisporphyrin host and the extended chiral diamines guest, which results large unidirectional twisting of two porphyrin units to accommodate the guests having preorganized binding sites with minimum host guest steric interactions. It is interesting to note that 1.DPEA((R,R)) and 1.DPEApy((R,R)) show CD signal opposite in sign to each other, which happens to be the case between 1.CHDA((S,S)) and 1.CHDApy((S,S)) also.