基于联萘二胺骨架的新型手性硫脲催化剂的合成

以C2轴手性化合物(S)-1,1′-联萘-2,2′-胺和手性氨基醇为原料,经乙酰化、甲基化、水解等反应合成了3种新型的手性硫脲催化剂,其结构经^1H NMR,¹³C NMR、 IR和HR-MS(ESI)表征。     

联萘衍生物的N M R表征Ⅱ.2,2＇-(3,4-四酸二酐)二苯甲酰氧基-1,1＇联萘

用一维1HNMR、13CNMR方法研究了 2,2＇-(3,4-四酸二酐)二苯甲酰氧基-1,1＇联萘的结构,并通过二维1H-1H同核相关、13C-1HH异核相关及13C-1H异核远程相关谱进一步地确定其1H谱和13C谱中各谱峰的归属,为同类化合物的表征提供了依据.     

1,1′-联萘化合物的氧化偶联合成

评述了β-萘酚序列化合物在铜胺络合物、硫酸铜、铁盐、氧钒络合物等作用下,直接氧化偶联合成1,1′-联萘化合物的路线,讨论了反应机理.     

1,1'-联萘化合物的氧化偶联合成

联二萘;不对称合成;氧化偶化;综述;1;1'-联萘化合物的氧化偶联合成     

基于1,1'-联-2-萘酚衍生物的手性荧光传感器

具有光活性的1,1′-联-2-萘酚（BINOL）衍生物是近年来研究较多的C2轴不对称芳香化合物,不仅具有很强的手性诱导作用,而且在适合结构基团修饰下能产生很强的荧光,可作为一类有效而灵敏的荧光化学传感器。在与手性胺、氨基醇、氨基酸、α-羟基羧酸、手性醇和单糖等手性有机化合物作用时,该荧光化学传感器在不同识别位点接受客体分子、通过光诱导电子转移（PET）及电子交换能量转移（EET）等引起共轭高分子内能级发生变化,使得所有这些相互作用十分灵敏地在其发光强度和能量上反映出来,具体表现在化学传感器荧光增强与减弱或发射波长的变化上。本文总结了近年来1,1′-联-2-萘酚衍生物的荧光化学传感器在手性异构体识别领域的最新研究进展。     

(R)-1,1''''-联萘手性单元通过溶胶凝胶法合成杂化硅干凝胶

0IntroductionSol鄄gel鄄derivedhybridorganic鄄inorganicmateri鄄alsarereceivingmuchattentionsincetheycanexhib鄄itpropertiesassociatedwithboththeorganicmoieties(optical,electrical,molecularimprinting)andinorgan鄄icamorphousframework(porosity,hydrophilicity)[     

高效液相色谱法测定1,1’-联萘-2,2’-二酚的光学纯度

用高效液相色谱法测定了1,1’-联禁-2,2’-二酚的光学纯度。色谱柱:Si-5柱,流动相:石油醚／乙醇（93／7,V／V）。方法简便、快速、准确,准确度为98.6％～101.6％,相对平均偏差为1.01％。     

含多个(R)-1,1''''-联萘手性高分子合成与结构表征

单体（R）．3，3＇-二碘-2，2＇-二正丁氧基-1，1＇-联萘（（R）-M-1），（R）-6，6＇-二溴-2，2＇-二正丁氧基-1，1’-联萘（（R）-M-2）分别与1，4-二乙烯基-2，3-二丁氧基萘（M-3），在钯催化下，通过Heck交叉耦合反应合成手性高分子P-1与P-2．单体和高分子进行了^1H—NMR、^13C-NMR、FT-IR、旋光度、GPC、UV、热分析、荧光光谱和CD等测试分析．高分子侧链上引入丁氧基后使得手性高分子溶解性增强并具有良好的成膜性，手性高分子P-1和P-2都能发射较强的蓝绿色荧光，荧光量子效率分别为0．42和0．48．     

1,1′-联萘-2,2′-二胺的合成及在不对称合成中的应用

综述了 1,1′ 联萘 2 ,2′ 二胺 (联萘胺 )化合物的制备 ,讨论了它们作为手性辅助基或配体在烯烃、酮、亚胺的不对称氢化及在烯烃的不对称环丙烷化、醛的烷基化反应、醛的不对称烯丙基化反应、不对称烯丙位取代反应和不对称Diels Alder反应等反应中的应用 .     

含多个(R)-1,1′-联萘手性高分子合成与结构表征

单体(R)-3,3′-二碘-2,2′-二正丁氧基-1,1′-联萘((R)-M-1),(R)-6,6′-二溴-2,2′-二正丁氧基-1,1′-联萘((R)-M-2)分别与1,4-二乙烯基-2,3-二丁氧基萘(M-3),在钯催化下,通过Heck交叉耦合反应合成手性高分子P-1与P-2.单体和高分子进行了1H-NMR1、3C-NMR、FT-IR、旋光度、GPC、UV、热分析、荧光光谱和CD等测试分析.高分子侧链上引入丁氧基后使得手性高分子溶解性增强并具有良好的成膜性,手性高分子P-1和P-2都能发射较强的蓝绿色荧光,荧光量子效率分别为0.42和0.48.     

Synthesis and Enantioselective Discrimination of Chiral Fluorescence Receptors Bearing Amino Acid Units

Two chiral fluorescence receptors （1, 2） were synthesized, and their structures were characterized by IR, ^1H NMR, ^13C NMR, mass spectra and elemental analysis. The chiral recognition of receptors was studied by ^1H NMR and fluorescence spectra. The results demonstrate that receptors and dibenzoyl tartrate anion formed a 1 ： 1 complex. The receptor 1 exhibited a good enantioselective recognition ability toward the enantiomers of dibenzoyl tartrate anion.     

阴离子荧光受体研究进展

本文总结了近年来阴离子荧光受体的研究进展和荧光化学传感的主要机理,主要 介绍以下3类受体的设计合成及其在阴离子识别中的应用:(1)以氢键或静电作用键合阴 离子的受体(包括酰胺、脲及硫脲、胍盐和硫脲盐、五员杂环);(2)含金属和路易斯酸的受体;(3)以竞争键合机制识别阴离子的"化学传感体系".     

基于酰胺的荧光双冠醚阴离子受体的合成和识别性能研究

合成了一种带有荧光基团蒽的酰胺型双冠醚阴离子受体3. 用荧光光谱、紫外-可见吸收光谱及核磁共振氢谱研究了其与F^－, Cl^－, Br^－, I^－, H₂PO₄^－, AcO^－离子的相互作用, 结果表明3只对F^－具有很好的选择性识别能力, 并形成配合比为1∶2的络合物, 通过荧光发射强度计算出主体3与F^－间的相互作用时的结合常数.     

含氨基酸单元的手性主体的合成及手性识别研究

以L-丙氨酸和2,7-二萘酚为原料通过简单的方法合成了二种带有荧光基团萘的手性阴离子主体(1和2), 用红外光谱、质谱、元素分析、核磁共振氢谱及碳谱表征了它们的结构. 用荧光光谱及核磁共振氢谱研究了主体与二苯甲酰酒石酸阴离子的相互作用, 结果表明1, 2与D-或L-二苯甲酰酒石酸阴离子均形成1∶1的配合物, 主体1展现出良好的对二苯甲酰酒石酸阴离子对映选择性识别能力.     

Bidentate Chiral Bis(imidazolium)‐Based Halogen‐Bond Donors: Synthesis and Applications in Enantioselective Recognition and Catalysis

Even though halogen bonding—the noncovalent interaction between electrophilic halogen substituents and Lewis bases—has now been established in molecular recognition and catalysis, its use in enantioselective processes is still very rarely explored. Herein, we present the synthesis of chiral bidentate halogen‐bond donors based on two iodoimidazolium units with rigidly attached chiral sidearms. With these Lewis acids, chiral recognition of a racemic diamine is achieved in NMR studies. DFT calculations support a 1:1 interaction of the halogen‐bond donor with both enantiomers and indicate that the chiral recognition is based on a different spatial orientation of the Lewis bases in the halogen‐bonded complexes. In addition, moderate enantioselectivity is achieved in a Mukaiyama aldol reaction with a preorganized variant of the chiral halogen‐bond donor. This represents the first case in which asymmetric induction was realized with a pure halogen‐bond donor lacking any additional active functional groups.     

人工合成受体的阴离子识别研究(Ⅳ)——含有酚羟基化合物的设计合成及阴离子识别研究

Novel azine based receptors with phenolic hydroxyl groups have been synthesized and characterized. A remarkable color change was observed from ¹H NMR and UV-Vis titrations upon the addition of fluoride ions to the solution of receptors in DMSO. The addition of chloride, bromide and iodide to the receptors did not induce any change. The UV-Vis data indicate that a 1∶1 stoichiometry complex is formed between receptors and F^-. ¹H NMR titrations and solvation effect confirmed hydrogen interaction between the receptors and anion. Hence, the receptors bearing phenolic hydroxyl groups can act as fluoride ion sensors even in the presence of other hahide ions.     

含有酚羟基的吖嗪类荧光探针的阴离子识别与传感研究

设计合成了含有酚羟基的萘吖嗪类荧光探针分子,利用紫外-可见吸收光谱和荧光发射光谱研究了探针分子的阴离子识别和光化学传感性能。研究结果表明,该探针分子可以通过比色（紫外-可见吸收光谱）和荧光发射光谱双通道识别检测氟离子。该探针分子是一类比率型阴离子荧光探针,作用方式为探针分子酚羟基的去质子化作用,这种激发态质子转移（ESIPT）是探针分子呈现比率荧光特性的原因。通过本实验不但可以让学生掌握紫外-可见吸收光谱和荧光发射光谱仪的使用方法,还能培养学生在分子识别与光化学传感领域的科研兴趣。     

NMR characterization of 1,1′‐binaphthyl‐2,2′‐diyl hydrogen phosphate binding to chiral molecular micelles

NMR spectroscopy was used to characterize the binding of the chiral compound 1,1′‐binaphthyl‐2,2′‐diyl hydrogen phosphate (BNP) to five molecular micelles with chiral dipeptide headgroups. Molecular micelles have covalent linkages between the surfactant monomers and are used as chiral mobile phase modifiers in electrokinetic chromatography. Nuclear overhauser enhancement spectroscopy (NOESY) analyses of (S)‐BNP:molecular micelle mixtures showed that in each solution the (S)‐BNP interacted predominately with the N‐terminal amino acid of the molecular micelle's dipeptide headgroup. NOESY spectra were also used to generate group binding maps for (S)‐BNP:molecular micelle mixtures. In these maps, percentages are assigned to the (S)‐BNP protons to represent the relative strengths of their interactions with a specified molecular micelle proton. All maps showed that (S)‐BNP inserted into a previously reported chiral groove formed between the molecular micelle's dipeptide headgroup and hydrocarbon chain. In the resulting intermolecular complexes, the (S)‐BNP protons nearest to the analyte phosphate group were found to point toward the N‐terminal Hα proton of the molecular micelle headgroup. Finally, pulsed field gradient NMR diffusion experiments were used to measure association constants for (R) and (S)‐BNP binding to each molecular micelle. These K values were then used to calculate the differences in the enantiomers' free energies of binding, Δ(ΔG). The NMR‐derived Δ(ΔG) values were found to scale linearly with electrokinetic chromatography (EKC) chiral selectivities from the literature. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of Novel Chiral Biphenylamine Ligand 6,6'‐Dimethoxy‐2,2′‐diaminobiphenyl

A new chiral ligand 6,6′‐dimethoxy‐2,2′‐diaminobiphenyl was successfully prepared from 3‐nitrophenol via iodination, Ullmann coupling, and reduction. The resolving reagent (2R, 3R)‐ or (2S,3S)‐2,3‐di (phenylaminocarbonyl)tartaric acid was prepared from commercially available tartaric acid in large scale and was used to resolve the racemic 6,6′‐dimethoxy‐2,2′‐diaminobiphenyl. The chiral 6,6′‐ dimethoxy‐2,2′‐diaminobiphenyl obtained was proved to be enantiomerically pure.     

Synthesis of Novel Anionic Receptors with （Thio）urea and Amide Binding Sites and the Recognition Properties for Anions

IntroductionSincemoreandmoreanionsplayanimportantroleinbiologicalandchemicalprocesses ,thedesignandsynthe sisofreceptorsforon lineandrealtimedetectionofbio logicallyimportantanions ,andforenvironmentalmonitor ingofharmfulanionpollutantshaveattractedparticularat tentioninsupramolecularchemistry .1Thebasicstrategyfortheconstructionofanion bindingreceptorsistoexploitthereceptorsthathaveelectrostatic ,2 hydrogenbonding ,3orLewisacidiccentralinteraction .4 Amongavarietyofnon covalentinteractions ,h…