(R,R)-1,2-diaminocyclohexane tartrate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R,R)-1,2-diaminocyclohexane tartrate
• 英文别名: [(1R,2R)-2-azaniumylcyclohexyl]azanium;2,3-dihydroxybutanedioate
• 化学式: C₄H₆O₆*C₆H₁₄N₂
• 分子量: 264.279
• InChiKey: GDOTUTAQOJUZOF-KGZKBUQUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.91
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  167
• 氢给体数：
  6
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (R,R)-1,2-diaminocyclohexane tartrate 在 palladium 10% on activated carbon 、 氢气 、 碳酸氢钠 、 对甲苯磺酸 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 114.0h， 生成 1-((1R,2R)-2-(1H-benzo[d]imidazol-1-yl)cyclohexyl)-1H-benzo[d]imidazole
  参考文献：
  名称：

  Synthesis, structure, and catalytic activity of palladium complexes with new chiral cyclohexane-1,2-based di-NHC-ligands

  摘要：

  A pair of novel palladium complexes {[(1S,2S)-L]PdBr2} and {[(1R,2R)-L]PdBr2} of chiral di-N-heterocyclic carbene ligands derived from chiral 1,2-cyclohexanediamine have been prepared in moderate to good yields and characterized by NMR, HRMS and X-ray single crystal diffraction studies. The obtained chiral NHC-Pd compound was able to catalyze the asymmetric Suzuki-Miyaura couplings of aryl bromides with arylboronic acids in good yields and moderate enantioselectivities (up to 61% ee). (C) 2012 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2011.12.008
• 作为产物：
  描述：

  D-酒石酸 、 1,2-二氨基环己烷 在 溶剂黄146 作用下， 以 水 为溶剂， 以99%的产率得到(R,R)-1,2-diaminocyclohexane tartrate
  参考文献：
  名称：

  A Practical Method for the Large-Scale Preparation of [N,N'-Bis(3,5-di-tertbutylsalicylidene)-1,2-cyclohexanediaminato(2-)]manganese(III) chloride, a Highly Enantioselective Epoxidation Catalyst

  摘要：

  DOI：

  10.1021/jo00086a062

文献信息

• One catalyst for two distinct reactions: sequential asymmetric hetero Diels–Alder reaction and diethylzinc addition
  作者：Haifeng Du、Xue Zhang、Zheng Wang、Kuiling Ding

  DOI：10.1016/j.tet.2005.08.007

  日期：2005.10

  addition to the benzaldehyde, affording the corresponding secondary alcohol with up to 94.5% ee under optimized conditions. On the basis of these facts, the integration of two distinct enantioselective reactions, HDA and diethylzinc addition reactions, has been realized in one-pot with the promotion of a single chiral zinc catalyst in a sequential manner. The impact of diimine additive on the catalytic system

  本文介绍了成功开发出一系列包含（R）-3,3'-Br 2 -BINOL配体和各种二亚胺活化剂的手性锌催化剂，通过组合方法使Danishefsky's二烯与醛的对映选择性HDA反应，得到相应的2 ，3-二氢-4 H-pyran-4-one衍生物，具有出色的收率和对映选择性。这类催化剂的应用范围也扩大到了苯甲醛中的二乙基锌加成反应，从而在优化的条件下得到了相应的仲醇，其ee含量高达94.5％。基于这些事实，已经实现了两个不同的对映选择性反应，即HDA和二乙基锌加成反应的整合，并且以顺序的方式促进了一种手性锌催化剂的整合。通过探索反应体系的非线性效应，研究了二亚胺添加剂对HDA反应催化体系的影响。催化体系中表现出的正非线性效应可归因于杂手性锌物质的不良溶解性。概述了Danishefsky二烯与醛的2- BINOL / Zn /二亚胺催化的对映选择性HDA反应。
• Resolution of RacemicN-Benzyl α-Amino Acids by Liquid-Liquid Extraction: A Practical Method Using a Lipophilic Chiral Cobalt(III) Salen Complex and Mechanistic Studies
  作者：Pawel Dzygiel、Toby B. Reeve、Umberto Piarulli、Martin Krupicka、Igor Tvaroska、Cesare Gennari

  DOI：10.1002/ejoc.200701101

  日期：2008.3

  efficient resolution of racemic N-benzyl α-amino acids (N-Bn-AA) has been achieved by a liquid-liquid extraction process using the lipophilic chiral salen–cobalt(III) complex [CoIII(3)(OAc)]. As a result of the resolution by extraction, one enantiomer (S) of the N-benzyl α-amino acid predominated in the aqueous phase, while the other enantiomer (R) was driven into the organic phase by complexation to cobalt

  外消旋 N-苄基 α-氨基酸 (N-Bn-AA) 的有效拆分是通过使用亲脂性手性 salen-钴 (III) 复合物 [CoIII(3)(OAc)] 的液-液萃取过程实现的。作为萃取拆分的结果，N-苄基α-氨基酸的一种对映体（S）在水相中占主导地位，而另一种对映体（R）通过与钴的络合而进入有机相。然后通过用甲醇中的连二亚硫酸钠水溶液或 L-抗坏血酸进行还原性 (CoIII → CoII) 反萃取，定量释放复合氨基酸 (R)。还原裂解允许以良好的收率回收 [CoII(3)] 复合物，该复合物可以很容易地用空气/AcOH 重新氧化为 [CoIII(3)(OAc)]，并在基本上不损失反应性和选择性的情况下重复使用。对氮取代的研究表明，氨基酸氮上单个苄基的存在对于在提取过程中获得高对映选择性很重要。还通过对映体交换实验研究了拆分过程的动力学与热力学性质，这表明 [CoIII(3)(OAc)] 的液
• [EN] SYNTHESIS OF CYCLIC CARBONATES<br/>[FR] SYNTHÈSE DE CARBONATES CYCLIQUES
  申请人：UNIV NEWCASTLE

  公开号：WO2009109765A1

  公开（公告）日：2009-09-11

  A dimeric aluminium(salen) catalyst of formula I: herein: Y-Q is CRC1=N or CRC1RC2-NRN1, where RC1, RC2 and RN1 are independently selected from H, halo, optionally substituted C1-20 alkyl, optionally substituted C5-20 aryl, ether and nitro; each of the substituents R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16, is independently selected from H, halo, optionally substituted C1-20 alkyl, optionally substituted C5-20 aryl, optionally substituted C3-20 heterocyclyl, ether and nitro; X1 and X2 are independently either (i) a C2-5 alkylene chain, which is optionally substituted by one or more groups selected from C1-4 alkyl and C5-7 aryl, or a C1-3 bisoxyalkylene chain, which is optionally substituted by one or more groups selected from C1-4 alkyl and C5-7 aryl or (ii) represent a divalent group selected from C5-7 arylene, C5-7 cyclic alkylene and C3-7 heterocyclylene, which may be optionally substituted; (i) (a) at least one of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 is selected from L-A, where L is a single bond or a C1-10 alkylene group and A is an ammonium group paired with a counterion selected from Cl, Br and I; and/or (b) at least one of X1 and X2 is a divalent C3-7 heterocyclene group, containing a ring atom which is a quaternary nitrogen atom paired with a counterion selected from Cl, Br and I; and/or (c) at least one of X1 and X2 is a C2-5 alkylene chain or a C1-3 bisoxyalkylene chain, substituted by a group -Q-L-A, where Q is either -C(=O)-O-, -C(=O)-NH-, or a single bond; and/or (ii) (a) one of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, and R16 is L-A', where L is as defined above and A' is a ammonium linking group bound to a solid support and paired with a counterion selected from Cl, Br and I; or (b) one of X1 and X2 is a divalent C3-7 heterocyclene group, containing a ring atom which is a quaternary nitrogen forming part of an ammonium linking group bound to a solid support and paired with a counterion selected from Cl, Br and I; or (c) one of X1 and X2 is a C2-5 alkylene chain or a C1-3 bisoxyalkylene chain, substituted by a group -Q-L-A'.

  一种二聚铝（salen）催化剂的化学式I：在此处：Y-Q是CRC1=N或CRC1RC2-NRN1，其中RC1、RC2和RN1分别独立选择自H、卤素、可选择性取代的C1-20烷基、可选择性取代的C5-20芳基、醚和硝基；R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15和R16中的每一个取代基都是独立选择自H、卤素、可选择性取代的C1-20烷基、可选择性取代的C5-20芳基、可选择性取代的C3-20杂环烷基、醚和硝基；X1和X2独立地是（i）C2-5烷基链，可选择性地通过一个或多个来自C1-4烷基和C5-7芳基的基团取代，或者是C1-3双氧烷基链，可选择性地通过一个或多个来自C1-4烷基和C5-7芳基的基团取代；或者（ii）代表可选择性取代的C5-7芳基、C5-7环烷基和C3-7杂环烷基中选取的二价基团；（i）（a）R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15和R16中至少一个选择自L-A，其中L是单键或C1-10烷基基团，A是与Cl、Br和I中选取的对离子配对的铵基；和/或（b）X1和X2中至少一个是含有一个环原子为季氮原子的三价C3-7杂环烷基团，配对的对离子为Cl、Br和I；和/或（c）X1和X2中至少一个是由基团-Q-L-A取代的C2-5烷基链或C1-3双氧烷基链，其中Q是-E(=O)-O-、-E(=O)-NH-或单键；和/或（ii）（a）R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15和R16中的一个是L-A'，其中L如上所定义，A'是与Cl、Br和I中选取的对离子配对的铵基固定在固体支撑上；或者（b）X1和X2中的一个是含有一个环原子为季氮原子构成铵基固定在固体支撑上的三价C3-7杂环烷基团，配对的对离子为Cl、Br和I；或者（c）X1和X2中的一个是由基团-Q-L-A'取代的C2-5烷基链或C1-3双氧烷基链。
• Synthesis, Coordination Chemistry and Bonding of Strong N-Donor Ligands Incorporating the 1<i>H</i>-Pyridin-(2<i>E</i>)-Ylidene (PYE) Motif
  作者：Qi Shi、Robert J. Thatcher、John Slattery、Pardeep S. Sauari、Adrian C. Whitwood、Patrick C. McGowan、Richard E. Douthwaite

  DOI：10.1002/chem.200901382

  日期：2009.10.26

  one to three PYE groups that coordinate to a metal through the exocyclic nitrogen atom of each PYE moiety, and the resulting metal complexes have been characterised by methods including single‐crystal X‐ray diffraction and NMR spectroscopy to examine metal–ligand bonding and ligand dynamics. Upon coordination of a PYE ligand to a proton or metal‐complex fragment, the solid‐state structures, NMR spectroscopy

  基于1 H吡啶（2 E制备了亚丙基（PYE）基序，包括非手性和手性实例。配体结合了一个到三个PYE基团，这些PYE基团通过每个PYE部分的环外氮原子与金属配位，并且所得的金属配合物已通过包括单晶X射线衍射和NMR光谱法的方法进行了表征，以检查金属-配体的键合和配体动力学。在将PYE配体与质子或金属络合物片段配位后，固态结构，NMR光谱和DFT研究表明，电荷重分布发生在PYE杂环内，这是吡啶鎓-酰胺型共振结构的贡献。额外的红外光谱和计算研究表明，PYE配体是强供体配体。 N键，突出杂环N-取代基在螯合配体的衍生物使限制运动的金属原子的附近。固态结构和DFT计算也显示出明显的空间拥堵以及金属与配体CH键之间的次生金属-配体相互作用。
• Chiral salen–metal complexes as novel catalysts for the asymmetric synthesis of α-amino acids under phase transfer catalysis conditions
  作者：Yuri N Belokon、Michael North、Tatiana D Churkina、Nikolai S Ikonnikov、Victor I Maleev

  DOI：10.1016/s0040-4020(01)00072-2

  日期：2001.3

  complexes have been tested as catalysts for the C-alkylation of Schiff's bases of alanine and glycine esters with alkyl bromides under phase-transfer conditions (solid sodium hydroxide, toluene, ambient temperature, 1–10 mol% of the catalyst). The best catalyst, which was derived from a Cu(II) complex of (1R, 2R or 1S,2S)-[N,N′-bis(2′-hydroxybenzylidene)]-1,2-diaminocyclohexane, gave α-amino and α-methyl-α-amino

  在相转移条件下（固体氢氧化钠，甲苯，环境温度，催化剂的1-10 mol％），手性salen-金属配合物已被用作催化剂，用于将希夫氏丙氨酸和甘氨酸酯与烷基溴进行C烷基化。 。最好的催化剂是由（1 R，2 R或1 S，2 S）-[ N，N'-双（2'-羟基亚苄基）]-1,2-二氨基环己烷的Cu（II）络合物衍生的，得到α-氨基和α-甲基-α-氨基酸，对映体过量为70-96％。