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101.
Boyle GA Govender T Kruger HG Maguire GE Naicker T 《Magnetic resonance in chemistry : MRC》2008,46(12):1089-1095
The NMR elucidation of a novel ligand (S)-pentacyclo-undecane bis-(4-phenyloxazoline) and related pentacyclo-undecane (PCU) derivatives is reported. Two-dimensional NMR proved to be a powerful technique in overcoming the difficulties associated with the elucidation of these compounds when only one-dimensional NMR data is utilized. A chiral substituent was introduced to both 'arms' of the PCU skeleton to produce derivatives 1-3. These derivatives display C(1) symmetry with all thecage atoms being nonequivalent. Owing to overlapping of peaks in the (1)H spectra, identification of these diastereomeric protons was very difficult. The (13)C spectra gave rise to clear splitting of the nonequivalent carbons. This is unusual compared to similar PCU derivatives with chiral substituents as splitting of all the diastereomeric cage carbons has not yet been reported. Nuclear Overhauser enhancement spectroscopy (NOESY) correlations of derivatives 1-3 confirm the different conformations of the molecule in which the side 'arms' occupy different orientations with respect to cage moiety. 相似文献
102.
Filippi A Speranza M Paladini A De Carolis R Guidoni AG Laganà A Satta M 《Journal of mass spectrometry : JMS》2006,41(1):98-102
Diastereomeric clusters of general formula [MAB(2)](+) and [MA(2)B](+) (M = Li(I), Na(I), Ag(I), Ni(II)-H, or Cu(II)-H; A = (R)-(-)- and (S)-(+)-(1-aminopropyl)phosphonic acid; B = (1R)-(-)- and (1S)-(+)-(1-aminohexyl)phosphonic acid) have been readily generated in the electrospray ionization (ESI) source of a triple-quadrupole mass spectrometer and their collision-induced dissociation (CID) investigated. CID of diastereomeric complexes, e.g. [MA(S)(B(S))(2)](+) and [MA(R)(B(S))(2)](+), leads to fragmentation patterns characterized by R(homo) = [MA(S)B(S)](+)/[M(B(S))(2)](+) and R(hetero) = [MA(R)B(S)](+)/[M(B(S))(2)](+) abundance ratios, which depend upon the relative stability of the diastereomeric [MA(S)B(S)](+) and [MA(R)B(S)](+) complexes in the gas phase. The chiral resolution factor R(chiral) = R(homo)/R(hetero) is found to depend not only on the nature of the M ion but also on that of the fragmenting species, whether [MAB(2)](+) or [MA(2)B](+). The origin of this behavior is discussed. 相似文献
103.
104.
The precise and stereocontrolled synthesis of the C9-C23 portion, the key mother spiroketal of the HIV-1 protease inhibitive didemnaketals from the ascidian Didemnum sp., has been carried out through multisteps starting from (R)-pulegone as the chiral template. This approach involved the distereoselective construction of eight chiral centers by intramolecular chiral inducement and the coupling of two fragments by Julia reaction. 相似文献
105.
106.
采用气相色谱-质谱联用技术(GC-MS),以N,O-双三甲基硅基三氟乙酰胺为衍生化试剂,系统研究了4种类固醇类环境内分泌干扰物雌酮(E1)、17β-雌二醇(E2)、雌三醇(E3)、17α-乙炔基雌二醇(EE2)的羟基衍生化行为,考察了BSTFA用量、衍生化温度和时间对类固醇类环境内分泌干扰物衍生化效果的影响以及衍生化产物的稳定性、标准曲线、仪器检出限等,并对衍生化产物特征碎片离子的裂解机理进行了解释.结果表明:对于100 μL 0.01 g/L标准混合溶液,BSTFA的最佳用量为25 μL;衍生化过程不需要加热,常温下(20 ℃)下反应10 min就可取得最佳的衍生化效果;衍生化产物的稳定性较好,在-20 ℃下放置48 h,相对响应因子RRF基本没有降低.在优化的实验条件下,各待测物具有良好的线性相关性,E1和E2的检出限为0.3 μg/L,EE2和E3的检出限为5 μg/L. 相似文献
107.
Merten C Barron LD Hecht L Johannessen C 《Angewandte Chemie (International ed. in English)》2011,50(42):9973-9976
Splitting it up: Excellent agreement between the experimental and the quantum-chemically simulated Raman optical activity (ROA) spectrum of (+)-poly(trityl methacrylate) shows that the polymer backbone adopts a left-handed helical conformation while the trityl side groups display a left-handed propeller conformation. Thus ROA can be used to determine the complete structure of synthetic chiral polymers in solution. 相似文献
108.
A chiral ligand exchange capillary electrophoresis (CLE-CE) method using Zn(II) as the central ion and l-4-hydroxyproline as the chiral ligand coordinating with γ-cyclodextrin (γ-CD) was developed for the enantioseparation of amino acids (AAs) and dipeptides. The effects of various separation parameters, including the pH of the running buffer, the ratio of Zn(II) to l-4-hydroxyproline, the concentration of complexes and cyclodextrins (CDs) were systematically investigated. After optimization, it has been found that eight pairs of labeled AAs and six pairs of labeled dipeptides could be baseline-separated with a running electrolyte of 100.0 mM boric acid, 5.0 mM ammonium acetate, 3.0 mM Zn(II), 6.0 mM l-hydroxyproline and 4.0 mM γ-CD at pH 8.2. The quantitation of AAs and dipeptides was conducted and good linearity (r2 ≥ 0.997) and favorable repeatability (RSD ≤ 3.6%) were obtained. Furthermore, the proposed method was applied in determining the enantiomeric purity of AAs and dipeptides. Meanwhile, the possible enantiorecognition mechanism based on the synergistic effect of chiral metal complexes and γ-CD was explored and discussed briefly. 相似文献
109.
A novel dihydroazepine-bridged BIPHEP phosphoramidite ligand with an amino acid moiety in the backbone was synthesized and evaluated in the Rh-catalyzed asymmetric hydrogenation. The scorpion tail-like amino acid backbone is capable of hydrogen bond formation and able to shift the rotamer composition of the biphenyl axis with the two scissor-like arms. Pivaloyl-l -valine was studied as chiral selector unit and compared with pivaloylglycine as the achiral reference substance. The enantiomerization barrier of the pivaloylglycine-modified biphenylamide was determined to be ΔG≠=110 kJ/mol. In the case of pivaloyl-l -valine, the (Sax) isomer is thermodynamically favored. Due to the relatively high barrier, the ligand is atropisomeric at room temperature and allows the preparative separation of the stereoisomers. The obtained phosphoramidite ligands were separated by chiral HPLC. For the first eluting rotamer, Rh complex ([Rh(cod)(L)2]BF4) was generated in situ and examined in the enantioselective hydrogenation of 2-acetamidoacrylate and methyl 2-acetamido-3-phenylacrylate, achieving enantiomeric excesses of up to 94 %. 相似文献
110.