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31.
Prochiral alkenes, aldehydes, and ketones constitute the most frequently used starting materials for enantioselective organic syntheses. Protocols often involve chiral binding agents or Lewis acids that can give two diastereomeric adducts, the ratios of which are measures of chiral recognition. With π adducts, the diastereomers differ in the enantioface of the C?C or O?C group bound to the Lewis acid. This review provides the first comprehensive analysis of such equilibria and related binding phenomena with chiral transition metal Lewis acids. An extensive body of data from the authors' laboratory for complexes of the pyramidal rhenium fragment [(η5?C5H5)Re(No)(PPh3)]+ ( I ) affords particular insight. Literature data for other complexes are also summarized. A general model for chiral recognition based upon the relative steric properties of four quadrants is presented. This enables binding selectivities to be individually and rationally optimized for different classes of ligands. Electronic effects are also identified and correlated with specific structural properties. Relationships between binding equilibria, reactivity, and product configurations are discussed. 相似文献
32.
Takeshi Kaneda 《Journal of fluorine chemistry》2005,126(1):17-26
Synthesis and synthetic utilities of stereocontrolled α,α-difluoro-β-hydroxy-γ,δ-unsaturated carbonyl compounds via enzymatic resolution with lipase PS (Pseudomonas cepacia, Amano Pharmaceutical Co. Ltd.) or lipase MY (Candida rugosa, Meito Sangyo Co. Ltd.) were described, and then the absolute configuration of obtained chiral materials was determined by the modified Mosher's method. 相似文献
33.
Reported here is an analytical method enabling the stereochemical resolution of a new antianginal compound possessing two stereogenic centers, leading to four stereoisomers. Only one of these isomers is currently under development as a novel antianginal agent and consequently, the other three isomers are considered as unwanted chiral impurities. Therefore, an enantioselective method is required in order to check its enantiomeric purity. This paper presents a method exploiting the high efficiency of capillary electrophoresis and the complexing properties of cyclodextrins to achieve the separation of the four stereoisomers of this weakly basic compound (pKa = 7.4). For this purpose, the combination of a neutral cyclodextrin, hydroxypropyl-gamma-cyclodextrin (HP-gamma-CD), and an anionic cyclodextrin, carboxymethyl-beta-cyclodextrin (CM-beta-CD), was added to the separation buffer running in an uncoated silica capillary. After selection of the suitable cyclodextrin system, satisfactorily separation conditions were as follows: 30 mM phosphate buffer (pH 6.4) containing 10 mM of HP-gamma-CD and 10 mM of CM-beta-CD, running voltage +30 kV. The resulting run time and resolutions were respectively about 17 min and between 1.95 and 2.84. Linearity curves (0.993 < r2 < 0.998) are also shown. 相似文献
34.
合成了9种具L-氨基酸衍生物结构的介晶化合物(I-Ⅲ,Ⅳab,Ⅴa,b,Ⅵa,b)、4种氨基酸衍生物(A1-4)和6种介晶化合物(M1-6).新化合物(Ⅰ-Ⅲ,Ⅳa,b,Ⅴa,b,Ⅵa,b,A4,M3-6)的化学结构通过IR、1HNMR和元素分析证实;并用偏光显微观察和DSC分析研究了其相变行为,结果表明有8种化合物(M3-6,Ⅵa,b,Ⅴb,Ⅵb)呈现液晶相变。测定了它们的比旋光度。通过X射线衍射研究了化合物Ⅵh120~130℃和Ⅵb170~180℃的近晶结构,Ⅵb显,Ⅵb呈。测定了化合物Ⅳb的电滞回线,证明其具铁电性。 相似文献
35.
从(-)-(1S,2R,4S)-5,6-二亚甲基双环[2.2.1]庚-2-醇(I)和(-)-(1S,2S,4S)-5,6-二亚甲基双环[2.2.1]庚-2-醇(Ⅱ)出发,合成了它们的醚类和取代苯甲酸酯类光学纯的衍生物。通过[α]D测定和构型分析,发现它们是含有3个手性碳(C1,C2和C4)的桥环化合物,其旋光性与构型的关系均符合可极化度多级圆球不对称性模型。 相似文献
36.
Masaaki Omote 《Tetrahedron letters》2005,46(2):319-322
A new axially dissymmetric ligand with large perfluoroalkyl groups, 2,2′-bis(1-hydroxy-1H-perfluorooctyl)biphenyl (1c), which could not be obtained by the coupling reaction of the aryl bromide using copper powder, was synthesized successfully by the coupling reaction using Ni(COD)2. This ligand showed much higher asymmetric induction in the reaction of diethylzinc with benzaldehyde than the trifluoromethyl (1a) or pentafluoroethyl (1b) analogues. 相似文献
37.
手性液晶聚硅氧烷毛细管柱的制备及应用 总被引:3,自引:0,他引:3
合成了一种手性液晶侧链的聚硅氧烷固定液,并涂制成毛细管柱,此柱适合于分离各种取代基的酚类异构体。对柱效和选择性进行了评价。 相似文献
38.
合成了新型手性Salen配体(H3L)及新型手性Salen双核锌配合物(主体).通过研究主体对咪唑类客体及氨基酸酯类客体的分子识别行为,测定了这些配位反应的缔合常数.主体对咪唑类客体分子识别的缔合常数顺序为:K(Im) >K(2-MeIm) >K(2-Et-4-MeIm).主体对氨基酸酯类客体分子识别的缔合常数顺序为:K(LeuOCH3) >K(ValOCH3) >K(AlaOCH3) >K(SerOCH3),配位数均为2.主体与D、 L型氨基酸酯分子识别反应在不同温度下的缔合常数结果表明,随着温度的升高,对映选择性下降.实验发现反应体系中存在焓熵补偿关系. CD光谱的研究结果也反映了主体对不同客体识别能力的差异. 相似文献
39.
Magnetic field-induced orientation of a chiral side chain liquid crystalline polyacrylate(P-11) was studied by using IR dichroism. For the investigated P-11, it has been shown thatthe magnetic alignment takes place over the entire temperature range between its meltingpoint and clearing point and the orientation level is strongly temperature-dependent, thedevelopment with time of the magnetic orieatation follows an exponeotial-type relation,and the smectic phase state influences the thermal relaxation process in the absence of themagnetic field. 相似文献
40.
Summary The simultaneous stereospecific assay of four stereoisomers of diltiazem hydrochloride in bulk drug and aqueous solution was
developed using HPLC on a Chiralcel OF column. The four isomers were quantitated with good precision by the internal standard
method. The chiral inversion of (+)-cis-diltiazem hydrochloride in vitro, stability of its (2S, 3S) configuration in the solid
and aqueous states was examined by HPLC. Chiral inversion of (+)-cis-diltiazem hydrochloride was not observed in the solid
state, and its (2S, 3S) configuration was stable to heat, humidity and light. Chiral inversion of (+)-cis-diltiazem hydrochloride
(2S, 3S) was observed in aqueous solution under UV, but not in aqueous solution stored at 80°C for 5h nor under visible light
for 10 h. The (+)-cis-diltiazem hydrochloride (2S, 3S) epimerized to (+)-trans-diltiazem hydrochloride (2R, 3S) with a half-life
of 5h in aqueous solution under UV but the reverse chiral inversion of (+)-trans-diltiazem hydrochloride (2R, 3S) to (+)-cis-diltiazem
hydrochloride (2S, 3S) was not observed. 相似文献