(1R,2R)-N¹,N²-bis(thiophen-2-ylmethyl)-cyclohexane-1,2-diamine

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (1R,2R)-N¹,N²-bis(thiophen-2-ylmethyl)-cyclohexane-1,2-diamine
• 英文别名: (1R,2R)-1-N,2-N-bis(thiophen-2-ylmethyl)cyclohexane-1,2-diamine
• 化学式: C₁₆H₂₂N₂S₂
• 分子量: 306.496
• InChiKey: NUEHZAHSWVRWIV-HZPDHXFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  80.5
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,2R)-N¹,N²-bis(thiophen-2-ylmethyl)-cyclohexane-1,2-diamine 、 zinc(II) chloride 以 乙醇 为溶剂， 反应 12.0h， 以85%的产率得到
  参考文献：
  名称：

  Synthesis and structural characterisation of zinc complexes bearing furanylmethyl and thiophenylmethyl derivatives of (R,R)-1,2-diaminocyclohexanes for stereoselective polymerisation of poly(rac-lactide)

  摘要：

  Novel dichloro zinc complexes based on enantiopure N,N-diamine ligands bearing furanylmethyl and thiophenylmethyl pendent groups were synthesised, and their crystal structures were determined using X-ray crystallography. The isopropoxide derivatives (generated in situ) of these well-characterised complexes efficiently catalysed the ring-opening polymerisation (ROP) of rac-lactide (rac-LA) at two different temperatures under controlled conditions. Highly heterotactic polylactide (PIA) was obtained with P-r = 0.80 at -25 degrees C in THF. Crown Copyright (C) 2014 Published by Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2014.03.055
• 作为产物：
  描述：

  trans-1,2-(R,R)-diammoniumcyclohexane tartrate 在 sodium tetrahydroborate 、 potassium carbonate 作用下， 以 乙醇 、 水 为溶剂， 反应 48.0h， 生成 (1R,2R)-N¹,N²-bis(thiophen-2-ylmethyl)-cyclohexane-1,2-diamine
  参考文献：
  名称：

  铱（I）催化芳族酮的不对称转移氢化的手性含硫配体

  摘要：

  新的高效催化剂体系，与IrCl（COD）PPh 3和手性[SNNS]型配体相结合，被用于在温和的反应条件下芳族酮的不对称转移加氢。以高收率和良好至优异的对映选择性（高达96％ee）获得相应的旋光醇。还制备并表征了具有[SNNS]型配体的手性Ir（I）配合物，其显示出良好的对映选择性和高活性。该反应可以在空气中进行，并且大大简化了催化实验。

  DOI：

  10.1016/j.tetasy.2007.08.016

文献信息

• Chiral sulfur-containing ligands for iridium(I)-catalyzed asymmetric transfer hydrogenation of aromatic ketones
  作者：Xue-Qin Zhang、Yan-Yun Li、Hui Zhang、Jing-Xing Gao

  DOI：10.1016/j.tetasy.2007.08.016

  日期：2007.9

  IrCl(COD)PPh3 and chiral [SNNS]-type ligands, were employed in the asymmetric transfer hydrogenation of aromatic ketones under mild reaction conditions. The corresponding optically active alcohols were obtained in high yield and good to excellent enantioselectivities (up to 96% ee). The chiral Ir(I) complexes with the ligands of [SNNS]-type were also prepared and characterized, which showed good enantioselectivity

  新的高效催化剂体系，与IrCl（COD）PPh 3和手性[SNNS]型配体相结合，被用于在温和的反应条件下芳族酮的不对称转移加氢。以高收率和良好至优异的对映选择性（高达96％ee）获得相应的旋光醇。还制备并表征了具有[SNNS]型配体的手性Ir（I）配合物，其显示出良好的对映选择性和高活性。该反应可以在空气中进行，并且大大简化了催化实验。
• Novel Chiral Diamino-Oligothiophenes as Valuable Ligands in Pd-Catalyzed Allylic Alkylations. On the “Primary” Role of “Secondary” Interactions in Asymmetric Catalysis
  作者：Vincenzo Giulio Albano、Marco Bandini、Manuela Melucci、Magda Monari、Fabio Piccinelli、Simona Tommasi、Achille Umani-Ronchi

  DOI：10.1002/adsc.200505109

  日期：2005.10

  A new class of chiral C2-symmetrical diamino-oligothiophenes is described to be effective in catalyzing Pd-mediated asymmetric allylic alkylations in a highly enantioselective manner. The combination of experimental as well as crystallographic evidence revealed the key role played by sulfur-based heteroaromatic rings in the stereodiscriminating step of the procedure. In particular, unprecedented non-covalent

  一种新型的手性C 2对称的二氨基-低聚噻吩被描述为以高对映选择性的方式有效催化Pd介导的不对称烯丙基烷基化反应。实验和晶体学证据的结合揭示了基于硫的杂芳族环在该方法的立体鉴别步骤中所起的关键作用。特别是，内部噻吩与金属中心之间空前的非共价二次相互作用被证明对于创造必要的立体化学环境至关重要，以确保出色的化学和光学收率。
• [EN] POLYDENTATE LIGANDS AND THEIR COMPLEXES FOR MOLECULAR CATALYSIS<br/>[FR] LIGANDS POLYDENTATES ET LEURS COMPLEXES POUR LA CATALYSE MOLÉCULAIRE
  申请人：LOS ALAMOS NAT SECURITY LLC

  公开号：WO2015191505A1

  公开（公告）日：2015-12-17

  The present invention relates generally to novel achiral and chiral sulfur-, nitrogen- and phosphorus-containing ligands, designated as NNS-type, P(0)NS-type, PNS-type, SNNS-type, SNNP(0)-type, or SNNP-type polydentate ligands and transition metal complexes of these ligands. The catalysts derived from these ligands and transition metal complexes may be used in a wide range of catalytic reactions, including hydrogenation and transfer hydrogenation of unsaturated organic compounds, dehydrogenation of alcohols and boranes, various dehydrogenative couplings, and other catalytic transformations.

  本发明涉及新型的无手性和手性硫、氮和磷含配体，被称为NNS型、P(0)NS型、PNS型、SNNS型、SNNP(0)型或SNNP型多齿配体以及这些配体的过渡金属配合物。从这些配体和过渡金属配合物衍生的催化剂可用于各种催化反应，包括不饱和有机化合物的加氢和转移加氢、醇和硼烷的脱氢、各种脱氢偶联反应以及其他催化转化。
• When is an imine not an imine? Unusual reactivity of a series of Cu(ii) imine-pyridine complexes and their exploitation for the Henry reaction
  作者：Christine J. Cooper、Matthew D. Jones、Simon K. Brayshaw、Benjamin Sonnex、Mark L. Russell、Mary F. Mahon、David R. Allan

  DOI：10.1039/c0dt01740j

  日期：——

  In this paper we report the synthesis and solid-state structures for a series of pyridine based Cu(II) complexes and preliminary data for the asymmetric Henry reaction. Interestingly, the solid-state structures indicate the incorporation of an alcohol into one of the imine groups of the ligand, forming a rare α-amino ether group. The complexes have been studied viasingle crystal X-ray diffraction,

  在本文中，我们报告了一系列分子的合成和固态结构 吡啶的Cu（II）配合物和不对称亨利反应的初步数据。有趣的是，固态结构表明醇结合到配体的亚胺基之一中，形成稀有的α-氨基醚基。已经通过单晶X射线衍射，EPR光谱和质谱研究了配合物。有趣的是，已观察到醇仅加成至亚胺部分之一。密度泛函理论（DFT）计算也已用于合理化观察到的结构。铜（II）配合物已在不对称亨利反应（苯甲醛 + 硝基甲烷 或者 硝基乙烷），而且ee的转化率高达84％，而且转化率高，非对映选择性中等。
• Nitroalkenes in the Ni(II) Catalyzed Asymmetric<i>Michael</i>Addition. Convenient Route to the Key Intermediate of Brivaracetam
  作者：Alexander N. Reznikov、Leonid E. Kapranov、Valentina V. Ivankina、Anastasiya E. Sibiryakova、Victor B. Rybakov、Yuri N. Klimochkin

  DOI：10.1002/hlca.201800170

  日期：2018.12

  A series of Ni(II) complexes with novel chiral ligands derived from (1R,2R)‐1,2‐diphenylethane‐1,2‐diamine was synthesized. The catalytic activity of these complexes in the asymmetric Michael reaction is demonstrated. Asymmetric addition of diethyl malonate to ω‐nitrostyrene and 1‐nitropent‐1‐ene in the presence of these complexes leads to the enantiomerically enriched diethyl (S)‐2‐(2‐nitro‐1‐phenylethyl)malonate

  合成了一系列具有新型手性配体的Ni（II）配合物，这些配体来自（1 R，2 R）-1,2-二苯乙烷-1,2-二胺。这些配合物在不对称迈克尔反应中的催化活性得到了证明。在这些络合物的存在下，将丙二酸二乙酯不对称添加到ω-硝基苯乙烯和1-硝基戊-1-烯中会导致对映异构体富集（S）-2-（2-硝基-1-苯乙基）丙二酸二乙酯（最高96％ee）和（R）2-（1-硝基戊基-2-基）丙二酸二乙酯（最高91％ee）。（4 R抗癫痫药布列西坦的关键中间体4-丙吡咯烷酮-2-酮是从相应的硝酸酯中获得的。