(R,R')-N-(3,5-di-tert-butylsalicylidene)-1,2-cyclo-hexanediaminehydrochloride | 821772-46-7

• 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: (R,R')-N-(3,5-di-tert-butylsalicylidene)-1,2-cyclo-hexanediaminehydrochloride
• 英文别名: (1R,2R)-2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)cyclohexanammonium chloride；[(1R,2R)-2-[(3,5-ditert-butyl-2-hydroxyphenyl)methylideneamino]cyclohexyl]azanium;chloride
• CAS: 821772-46-7
• 化学式: C₂₁H₃₄N₂O*ClH
• 分子量: 366.975
• InChiKey: IPSGMWMCCSMVGG-JAXOOIEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  58.6
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R,R')-N-(3,5-di-tert-butylsalicylidene)-1,2-cyclo-hexanediaminehydrochloride 在 sodium cyanoborohydride 、 溶剂黄146 、 三乙胺 作用下， 以 甲醇 为溶剂， 生成 (R,R)-N,N'-bis(3,5-di-tert-butylsalicyl)-1,2-diaminocyclohexane
  参考文献：
  名称：

  Electrochemical and Spectroscopic Effects of Mixed Substituents in Bis(phenolate)–Copper(II) Galactose Oxidase Model Complexes

  摘要：

  Nonsymmetric substitution of salen (1(R1,R2)) and reduced salen (2(R1,R2)) Cu-II-phenoxyl complexes with a combination of -Bu-t, -(SPr)-Pr-i, and -OMe substituents leads to dramatic differences in their redox and spectroscopic properties, providing insight into the influence of the cysteine-modified tyrosine cofactor in the enzyme galactose oxidase (GO). Using a modified Marcus-Hush analysis, the oxidized copper complexes are characterized as Class II mixed-valent due to the electronic differentiation between the two substituted phenolates. Sulfur K-edge X-ray absorption spectroscopy (XAS) assesses the degree of radical delocalization onto the single sulfur atom of nonsymmetric [1(tBu,SMe)](+) at 7%, consistent with other spectroscopic and electrochemical results that suggest preferential oxidation of the -SMe bearing phenolate. Estimates of the thermodynamic free energy difference between the two localized states (Delta G degrees) and reorganizational energies (lambda(R1R2)) of [1(R1,R2)](+) and [2(R1,R2)](+) lead to accurate predictions of the spectroscopically observed IVCT transition energies. Application of the modified Marcus-Hush analysis to GO using parameters determined for [2(R1,R2)](+) predicts a nu(max) of similar to 43600 cm(-1), well within the energy range of the broad Vis-NIR band displayed by the enzyme.

  DOI：

  10.1021/ja211247f
• 作为产物：
  描述：

  (1R,2R)-1,2-diaminocyclohexane 在 氯化铵 作用下， 以 甲醇 为溶剂， 反应 0.5h， 生成 (R,R')-N-(3,5-di-tert-butylsalicylidene)-1,2-cyclo-hexanediaminehydrochloride
  参考文献：
  名称：

  手性双核钛配合物催化氰化物环氧化物的不对称开环

  摘要：

  合成了一系列从水杨醛和3,3'-二甲酰基-BINOL获得的席夫碱。用的Ti（IV）这些席夫碱的复合物的活性与TMSCN环氧化物的不对称环开口。未纯化的配体的混合物被发现是作为最好的一个是有效的。还研究了温度，溶剂极性和预催化剂的结构改性对方法对映选择性的影响。

  DOI：

  10.1016/j.tetasy.2014.04.012

文献信息

• Chiral salen Cr(<scp>iii</scp>) complexes encapsulated in thermo-responsive polymer nanoreactors for asymmetric epoxidation of alkenes in water
  作者：Weiying Wang、Chaoping Li、Yibing Pi、Jiajun Wang、Rong Tan、Donghong Yin

  DOI：10.1039/c9cy01398a

  日期：——

  behaving as a quasi-homogeneous catalyst for the aqueous asymmetric epoxidation. Second, they effectively sequestered substrates from the surrounding environment, creating a highly concentrated environment for efficient catalysis. Third, water was excluded from the nanoreactor, minimizing the undesired hydrolysis of epoxides. As a result, the compartmentalized catalysts mediated aqueous asymmetric epoxidation

  手性Salen铬（III）（铬（沙仑））复合物通过折叠聚的两亲性无规共聚物（封装在热敏性聚合物纳米反应器Ñ -isopropylacrylamide-共-IL /铬（沙仑））（聚（NIPAAM-共-IL / Cr（salen））在水中的Cr（salen）附近。所得的催化纳米反应器与传统的Cr（salen）体系相比，在水中烯烃的不对称环氧化方面表现出一些优势。首先，将它们分散在水中，作为水不对称环氧化的准均相催化剂。其次，它们有效地隔离了周围环境中的底物，从而为高效催化创造了一个高度集中的环境。第三，将水从纳米反应器中排除，从而最大程度地减少了不希望的环氧化物水解。结果，间隔催化剂介导了水不对称环氧化，具有前所未有的收率（92–95％）和对映选择性（ee，92–99％），而传统的Cr（salen）催化剂的效率要低得多（4-12％的收率和29–44％ee）。而且，催化纳米反应器可通过热控分离方
• Asymmetric Copolymerization of CO₂with<i>meso</i>-Epoxides Mediated by Dinuclear Cobalt(III) Complexes: Unprecedented Enantioselectivity and Activity
  作者：Ye Liu、Wei-Min Ren、Jie Liu、Xiao-Bing Lu

  DOI：10.1002/anie.201305154

  日期：2013.10.25

  Unprecedented enantioselectivity and catalytic activity was observed in the asymmetric copolymerization of CO2 with meso‐epoxides (including the less reactive cyclopentene oxide) mediated by the dinuclear CoIII complex (S,S,S,S)‐1 under mild conditions. The resultant copolymers possess more than 99 % carbonate linkages and a perfectly isotactic structure.

  在温和条件下，由双核Co III配合物（S，S，S，S）-1介导的CO 2与内消旋环氧化合物（包括反应性较弱的环戊烯氧化物）的不对称共聚反应中观察到前所未有的对映选择性和催化活性。所得共聚物具有超过99％的碳酸酯键和完全等规的结构。
• Chiral Octahedral Complexes of Co^III As a Family of Asymmetric Catalysts Operating under Phase Transfer Conditions
  作者：Yuri N. Belokon、Victor I. Maleev、Michael North、Vladimir A. Larionov、Tat’yana F. Savel’yeva、Aike Nijland、Yuliya V. Nelyubina

  DOI：10.1021/cs400409d

  日期：2013.9.6

  Stereochemically inert and positively charged chiral complexes of CoIII prepared from Schiff bases derived from chiral diamines and salicylaldehydes were shown to be efficient catalysts of the asymmetric phase transfer benchmark reaction of alkylation of O’Donnell’s substrate with alkyl halides. The enantiomeric purities of the reaction products were up to 92%.

  由手性二胺和水杨醛衍生的席夫碱制备的Co III的立体化学惰性和带正电荷的手性配合物被证明是O'Donnell底物烷基卤化烷基化反应的不对称相转移基准反应的有效催化剂。反应产物的对映体纯度高达92％。
• Design and synthesis of binuclear Co-salen catalysts for the hydrolytic kinetic resolution of epoxides
  作者：Fengshou Wu、Kai Wang、Zaoying Li、Xunjin Zhu

  DOI：10.1016/j.catcom.2015.05.006

  日期：2015.8

  Co-salen complexes have further been evaluated in the hydrolytic kinetic resolution of racemic epoxides. And kinetic studies reveal that the binuclear Co-salen catalysts show a higher reactivity and better enantioselectivity in comparison to monometallic reference complex, indicating the two Co-salen units on the cyclic framework may work in a cooperative manner. Specifically, Co3, with the most flexible

  基于一系列具有不同环尺寸的亲水性环状骨架，合成了三种双核Co（III）-salen配合物。在外消旋环氧化物的水解动力学拆分中，还对Co-salen配合物的催化性能进行了评估。动力学研究表明，双核Co-salen催化剂与单金属参考配合物相比具有更高的反应性和更好的对映选择性，表明环状骨架上的两个Co-salen单元可能以协同方式起作用。具体而言，由于两个钴中心之间的有效协同相互作用，具有最灵活的环状骨架的Co3在三种催化剂中均表现出最佳的催化性能。
• Enantioselective Polymerization of Epoxides: A Highly Active and Selective Catalyst for the Preparation of Stereoregular Polyethers and Enantiopure Epoxides
  作者：Wataru Hirahata、Renee M. Thomas、Emil B. Lobkovsky、Geoffrey W. Coates

  DOI：10.1021/ja807709j

  日期：2008.12.31

  A chiral, bimetallic cobalt catalyst was discovered that is highly active and enantioselective for epoxide polymerization. The enantiomerically pure catalyst system exhibits a stereoselectivity factor (s = k(fast)/k(slow)) of 370 for propylene oxide, allowing enantiomerically pure epoxide to be recovered in nearly the maximum theoretical yield. In addition, the racemic catalyst forms highly isotactic

  发现了一种手性双金属钴催化剂，它对环氧化物聚合具有高活性和对映选择性。对映体纯催化剂体系对环氧丙烷的立体选择性因子 (s = k(fast)/k(slow)) 为 370，允许以接近最大理论产率回收对映体纯环氧化物。此外，外消旋催化剂以定量收率形成高度全同立构的聚(环氧丙烷)。该催化剂对其他环氧化物具有活性和选择性，例如 1- 氧化丁烯、1- 氧化己烯和氧化苯乙烯。