Solid-state optical properties of a chiral supramolecular fluorophore consisting of chiral (1R,2R)-1,2-diphenylethylenediamine and fluorescent carboxylic acid derivatives

By using (1R,2R)-1,2-diphenylethylenediamine as a chiral molecule and 2-anthracenecarboxylic acid as a fluorescent molecule, we created a chiral supramolecular organic fluorophore having circularly polarized luminescence properties in the solid-state.     

Understanding the catalytic role of flexible chiral δ-amino alcohols: the 1-(2-aminoethyl)norbornan-2-ol model

An empiric first approach to the knowledge about the structural factors influencing the catalytic behavior of conformationally flexible δ-amino-alcohol-based ligands, for the enantioselective addition of dialkylzincs to prochiral carbonyl groups, has been applied using the 1-(2-aminoethyl)norbornan-2-ol moiety as the model chiral system, and the asymmetrically catalyzed addition of diethylzinc to benzaldehyde as the test reaction. For this purpose, a selected small library of seven norbornane-based chiral ligands, bearing well-defined structural variations to allow a comparative study, that is, variation of the relative configuration and steric hindrance at the C(2), C(3) and/or C(7) norbornane positions, has been synthesized and probed in the mentioned test reaction. The experimental results obtained have been rationalized empirically using diastereomeric Noyori-like transition states, demonstrating that the conformational flexibility of the δ-amino-alcohol ligands, contrary to the more studied and rigid β-amino-alcohols, plays a crucial role on the catalytic behavior of such ligands (stereochemical sense and degree of the stereodifferentiation in the asymmetric process), which makes such structural factors, important for the improved design of new related chiral catalysts. In this sense, a robust crude empirical model for the prediction of the catalytic behavior of such δ-amino-alcohol-based ligands is proposed.     

Conformationally controlled (entropy effects), stereoselective vibrational quenching of singlet oxygen in the oxidative cleavage of oxazolidinone-functionalized enecarbamates through solvent and temperature variations

On photooxygenation (methylene blue as sensitizer) of E/Z enecarbamates, equipped with the oxazolidinone chiral auxiliary, the oxidative cleavage of the alkenyl functionality releases the enantiomerically enriched methyldesoxybenzoin (MDB) product. The extent (% ee) as well as the sense (R vs S) of the stereoselectivity in the MDB formation depends on the choice of the alkene configuration; the efficacy of stereocontrol may be tuned by appropriate solvent and temperature conditions. Highlighted is the finding that the formation of the preferred MDB enantiomer (R or S) depends for the E isomer on the chosen solvent and temperature, but not for the corresponding Z isomer. The activation parameters for the various solvents disclose that differential entropy effects (ΔΔS^‡) dominate the conformationally more flexible E diastereomers. As mechanistic rationale for this unprecedented conformationally imposed stereochemical behavior, we propose the competitive action of stereoselective vibrational quenching of the attacking singlet oxygen by the enecarbamate versus sterically controlled stereoselective oxidative cleavage of its double bond.     

Chiral separation of 1,1'-bi-2-naphthol and its analogue on molecular imprinting monolithic columns by HPLC

Two molecular imprinting polymer (MIP) monolithic columns with (S)-(-)-1,1'-bi-2-naphthol and (R)-(+)-5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol as the templating molecules, respectively, have been prepared by in situ polymerization using 4-vinylpyridine and ethylene dimethacrylate as functional monomer and cross-linker, respectively. The columns with good flow-through properties were obtained by changing the molar ratio of the functional monomer and the template molecule. The effects of mobile-phase composition on separation of enantiomers were systematically investigated. The results indicate that hydrophobic interaction in aqueous solution and hydrogen-bonding interaction in ACN between the enantiomers and polymers could play important roles in the retention and resolution. The effects of chromatographic conditions, such as flow rate, column temperature, sample loading, on the enantioseparation were also studied. Further, these two MIP columns show a cross-reactivity.     

Highly diastereoselective synthesis of bicyclo[4.2.0]octanone derivatives by the [2+2] photocycloaddition of chiral cyclohexenonecarboxylates to ethylene

The diastereoselective [2+2] photocycloaddition of a cyclohexenonecarboxylate containing (−)-8-(4-nitrophenyl)menthyl as a chiral auxiliary to ethylene gave the photocycloadduct, a bicyclo[4.2.0]octanone derivative, with a high degree of diastereoselectivity. A photoreaction, conducted in CH₂Cl₂ at −78 °C gave the corresponding photocycloadduct in 88% de. In the presence of Ti(OR)₄ or Me₃SnCl, the diastereoselectivity was increased up to 92% de.     

Optimization of the Synthesis of 2,6–Dinitro-4-trifluoromethylphenyl Ether Substituted Cyclodextrin Bonded Chiral Stationary Phases

The comparisons of five different chiral stationary phases (CSPs) based on 2,6-dinitro-4-trifluoromethylphenyl (DNP-TFM) ether substituted β-cyclodextrin are presented. The five CSPs differ from each other in the linkage/spacer chemistry, or on the position of the substituents on β-cyclodextrin, or in the sequence of the synthetic procedure. The results show that there are two optimum combinations: (1) DNP-TFM randomly substituted on the β-cyclodextrin as the chiral selector along with a carbamate linkage chain bonding it to the silica support; and (2) β-cyclodextrin derivatized by DNP-TFM substituents only on the C-2 and C-3 positions of the cyclodextrin with an ether linkage chain anchoring it to the silica gel. These two combinations show complementary separations for some enantiomers. The spacer chain effect is much more pronounced for the CSP based on the β-cyclodextrin derivatives with DNP-TFM substituents only on C-2 and C-3 positions than its randomly substituted counterpart. The sequence of derivatizing the cyclodextrin and attaching it to silica gel also affects its selectivity and efficiency. The β-cyclodextrin should be derivatized before it is linked to the silica gel.     

Chiral separations by capillary electromigration techniques in nonaqueous media. II. Enantioselective nonaqueous capillary electrochromatography

A review on the advantages, peculiarities, and the potential of enantioselective capillary electrochromatography (CEC) in nonaqueous media is presented. Some fundamentals on CEC with particular focus on enantioselective CEC are discussed. The strategies, concepts, preferentially utilized chiral selectors and column technologies that have been utilized to succeed in highly efficient enantiomer separations by nonaqueous CEC are described thoroughly.     

氰戊菊酯立体异构体在手性键合相上的分析

本文介绍了采用高效液相色谱法在(R)-N-3,5-二硝基苯甲酰苯甘氨酸手性键合相上氰戊菊酯的四个立体异构体的分离,以外消旋氰戊菊酯样品为参照,计算了光学活性氰戊菊酯样品的四个立体异构体的百分含量,确定了在手性键合相上氰戊菊酯四个立体异构体构型的流出顺序为SR→RS→SS→RR。     

淫羊藿根与叶活性成分的分析和比较

采用细胞膜色谱法（ＣＭＣ）筛选，并结合离体药理实验确定主要活性成分，利用高效液相色谱法分析比较了淫羊藿根与叶中的活性成分及其差异性．色谱条件为Ｋｒｏｍａｓｉｌ ＯＤＳ 柱（１５０ ｍｍ× ４．６ ｍｍ．Ｉ．Ｄ ）流动相甲醇－水（７０：３０，Ｖ：Ｖ）；检测波长２７０ｎｍ。筛选发现淫羊藿根中的两个有效成分ＹＹＨ－２１４和ＹＹＨ－２１６对血管有较强的舒张作用，表明活性成分在ＣＭＣ模型体系中的保留特性与药理作用之间存在良好的相关性。在此色谱条件下淫羊藿叶未检测到这两种活性成分．