N,N'-bis(3,5-dichloro-2-hydroxybenzyl)-trans-(R,R)-1,2-diaminocyclohexane | 859504-61-3

• 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: N,N'-bis(3,5-dichloro-2-hydroxybenzyl)-trans-(R,R)-1,2-diaminocyclohexane
• 英文别名: 2,4-dichloro-6-[[[(1R,2R)-2-[(3,5-dichloro-2-hydroxyphenyl)methylamino]cyclohexyl]amino]methyl]phenol
• CAS: 859504-61-3
• 化学式: C₂₀H₂₂Cl₄N₂O₂
• 分子量: 464.219
• InChiKey: UEMSHCJMNHHAHV-QZTJIDSGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  64.5
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N,N'-bis(3,5-dichloro-2-hydroxybenzyl)-trans-(R,R)-1,2-diaminocyclohexane 、 titanium(IV) (R)-sec-butoxide 以 乙醚 为溶剂， 以44.1%的产率得到Δ-[(R,R)-N,N'-bis(3,5-dichloro-2-hydroxybenzyl)-trans-1,2-diaminocyclohexane(-2H)]Ti((R)-sec-butoxido)2]
  参考文献：
  名称：

  Chiral-at-metal tetrahydrosalen complexes of resolved titanium(IV) sec-butoxides: Ligand wrapping and multiple asymmetric catalytic induction

  摘要：

  The reaction of the racemic and resolved tetrahydrosalen derivative LH2 (LH2 = N,N'-bis(3,5-dichloro-2-hydroxybenzyl)-trans-1,2-diaminocyclohexane) with the resolved titanium(IV) sec-butoxides Ti(OR-2Bu)(4) or Ti(OS-2Bu)(4) yielded a series of four compounds, LTi((OBu)-Bu-2)(2) (1-4), which have been characterized by IR, elemental analysis, H-1 and C-13 NMR and X-ray crystallography. X-ray crystallography revealed the co-crystallization of two pseudo-C-2-symmetric products from racemic LH2, whereas a perfect chiral induction of the ligand to the metal occurred when resolved (R,R)-LH2 was used, resulting in a Delta fac-fac wrapping mode of the tetradentate ligand about the titanium center. Ab initio electronic structure calculations (DFT) are in agreement that the lowest energy isomer is that which is experimentally observed. Catalysis screenings show that Ti(OS-2Bu)(4), in conjunction with (R,R)-LH2, forms a matched pair that catalyzes the addition of dimethyl zinc to benzaldehyde with higher enantioselectivity than that observed for resolved (R,R)-LH2 with Ti(OR-2Bu)(4) or achiral Ti((OPr)-Pr-i)(4). Increasing the temperature of the system results in slightly increased enantiomeric excess. (C) 2009 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2009.02.016
• 作为产物：
  描述：

  聚合甲醛 、 2,4-二氯酚 、 trans-1,2-Diaminocyclohexane 在 溶剂黄146 、 sodium tetrahydroborate 作用下， 以 乙腈 为溶剂， 反应 0.5h， 生成 N,N'-bis(3,5-dichloro-2-hydroxybenzyl)-trans-(R,R)-1,2-diaminocyclohexane
  参考文献：
  名称：

  手性Salan铝乙基配合物及其在丙交酯聚合中的应用

  摘要：

  手性四齿苯氧胺（salan-型）配体支持的铝乙基络合物的合成途径[Al（OC 6 H 2（R-6-R-4）CH 2）2 {CH 3 N（C 6 H 10）NCH 3 } -C 2 ħ 5 ]（4，7：R = H; 5，8：R =氯; 6，9：R = CH 3）的报告。在环己烷环上具有（R，R）构型的对映体纯的salan配体1-3提供了配合物4，5，和6 2个非对映异构（作为混合物一和b）。通过X射线分析确定，每个非对映异构体a为固态的五配位铝中心核，呈顺式（O，O）和顺式（Me，Me）配体几何结构。根据220-335 K温度范围内的变温（VT）1 H NMR ，220 K下1 H- 1 H NOESY的结果以及扩散有序光谱法（DOSY）得出的结论是，每个非对映异构体b也是具有五配位铝中心核的单体。几何形状是正方形锥体之间中间体与顺式- （O，O），反式- （ME，ME）配位体配置和三角双锥与反式-

  DOI：

  10.1002/chem.200900799

文献信息

• Chiral Salan Aluminium Ethyl Complexes and Their Application in Lactide Polymerization
  作者：Hongzhi Du、Aldrik H. Velders、Pieter J. Dijkstra、Jingru Sun、Zhiyuan Zhong、Xuesi Chen、Jan Feijen

  DOI：10.1002/chem.200900799

  日期：2009.9.28

  state, adopting a cis‐(O,O) and cis‐(Me,Me) ligand geometry. From the results of variable‐temperature (VT) 1H NMR in the temperature range of 220–335 K, 1H–1H NOESY at 220 K, and diffusion‐ordered spectroscopy (DOSY), it is concluded that each diastereoisomer b is also monomeric with a five‐coordinated aluminium central core. The geometry is intermediate between square pyramidal with a cis‐(O,O), trans‐(Me

  手性四齿苯氧胺（salan-型）配体支持的铝乙基络合物的合成途径[Al（OC 6 H 2（R-6-R-4）CH 2）2 CH 3 N（C 6 H 10）NCH 3 } -C 2 ħ 5 ]（4，7：R = H; 5，8：R =氯; 6，9：R = CH 3）的报告。在环己烷环上具有（R，R）构型的对映体纯的salan配体1-3提供了配合物4，5，和6 2个非对映异构（作为混合物一和b）。通过X射线分析确定，每个非对映异构体a为固态的五配位铝中心核，呈顺式（O，O）和顺式（Me，Me）配体几何结构。根据220-335 K温度范围内的变温（VT）1 H NMR ，220 K下1 H- 1 H NOESY的结果以及扩散有序光谱法（DOSY）得出的结论是，每个非对映异构体b也是具有五配位铝中心核的单体。几何形状是正方形锥体之间中间体与顺式- （O，O），反式- （ME，ME）配位体配置和三角双锥与反式-
• Diastereoisomerically Selective Enantiomerically Pure Titanium Complexes of Salan Ligands:  Synthesis, Structure, and Preliminary Activity Studies
  作者：Adi Yeori、Stanislav Groysman、Israel Goldberg、Moshe Kol

  DOI：10.1021/ic050745b

  日期：2005.6.1

  The degree of diastereoselectivity in the wrapping of four new chiral Salan ligands to form chiral-at-metal titanium complexes ranged from mild to perfect as a function of the ligands' N substituents; the enantiomerically pure complexes catalyzed the addition of diethyl zinc to benzaldehyde in 73-76% enantiomeric excess.

  四个新的手性Salan配体包裹形成金属手性钛配合物的非对映选择性程度取决于配体的N取代基，从轻度到完美。对映体纯的配合物催化二乙基锌加到苯甲醛中的对映体过量为73-76％。
• Chiral-at-metal tetrahydrosalen complexes of resolved titanium(IV) sec-butoxides: Ligand wrapping and multiple asymmetric catalytic induction
  作者：Samantha N. MacMillan、Christine F. Jung、Tamila Shalumova、Joseph M. Tanski

  DOI：10.1016/j.ica.2009.02.016

  日期：2009.7

  The reaction of the racemic and resolved tetrahydrosalen derivative LH2 (LH2 = N,N'-bis(3,5-dichloro-2-hydroxybenzyl)-trans-1,2-diaminocyclohexane) with the resolved titanium(IV) sec-butoxides Ti(OR-2Bu)(4) or Ti(OS-2Bu)(4) yielded a series of four compounds, LTi((OBu)-Bu-2)(2) (1-4), which have been characterized by IR, elemental analysis, H-1 and C-13 NMR and X-ray crystallography. X-ray crystallography revealed the co-crystallization of two pseudo-C-2-symmetric products from racemic LH2, whereas a perfect chiral induction of the ligand to the metal occurred when resolved (R,R)-LH2 was used, resulting in a Delta fac-fac wrapping mode of the tetradentate ligand about the titanium center. Ab initio electronic structure calculations (DFT) are in agreement that the lowest energy isomer is that which is experimentally observed. Catalysis screenings show that Ti(OS-2Bu)(4), in conjunction with (R,R)-LH2, forms a matched pair that catalyzes the addition of dimethyl zinc to benzaldehyde with higher enantioselectivity than that observed for resolved (R,R)-LH2 with Ti(OR-2Bu)(4) or achiral Ti((OPr)-Pr-i)(4). Increasing the temperature of the system results in slightly increased enantiomeric excess. (C) 2009 Elsevier B. V. All rights reserved.