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51.
The structural analysis of amylose tris(3,5-dimethylphenylcarbamate) (ADMPC) was performed by NMR spectroscopy using a sample with a lower degree of polymerization in order to understand the chiral recognition mechanism when it was used as a chiral stationary phase (CSP) in high-performance liquid chromatography (HPLC). ADMPC exhibited chiral discrimination for many enantiomers, including 1-(9-anthryl)-2,2,2-trifluoroethanol (1) and 1,1'-bi-2-naphthol (2) in both NMR and HPLC. A good agreement was observed between the HPLC and NMR results when chloroform was employed as the common solvent. The structure of ADMPC in solution was investigated by NMR using the 2D NOESY technique coupled with computer modeling, and a left-handed 4/3 helical structure was obtained as the most probable one. The binding geometry between ADMPC and the enantiomers of 1 was also investigated by (1)H NMR titration. On the basis of these results combined with molecular modeling, a rational model to explain the chiral discrimination mechanism of 1 on ADMPC was proposed. 相似文献
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Inoue IH Watanabe M Kinoshita T Kakizaki A Kato R Kobayashi A Kobayashi H Fujimori A 《Physical review. B, Condensed matter》1993,47(19):12917-12920
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Diastereoselective preparation and characterization of ruthenium bis(bipyridine) sulfoxide complexes
A new concept in the synthesis of optically active octahedral ruthenium complexes was realized for the first time when cis- or trans-Ru(bpy)2Cl, (cis- or trans-1) was reacted with either (R)-(+)- or (S)-(-)-methyl p-tolyl sulfoxide (2 or 3); this novel asymmetric synthesis leads to the diastereoselective formation of the ruthenium bis(bipyridine) complex cis-delta-[Ru(bpy)2(2)Cl]Cl (4) (49.6% de) or cis-lambda-[Ru(bpy)2(3)Cl]Cl (5) (48.4% de), respectively. cis- or trans-Ru(dmbpy)2Cl2 (cis- or trans-6) (dmbpy = 4,4'-dimethyl-2,2'-bipyridine) also reacts with 2 or 3, leading to the diastereoselective formation of cis-delta-[Ru(dmbpy)2(2)Cl]Cl (7) (59.5% de) or cis-lambda-[Ru(dmbpy)2(3)Cl]Cl (8) (57.2% de), respectively. The diastereoselectivity of these reactions is governed solely by the chirality of the sulfoxide nucleophile. This represents the first process by which a sigma-bonded ligand occupying only a single coordination site has had such an important influence on the stereochemical outcome of a ruthenium bis(bipyridine) complex formation. These novel complexes were fully characterized by elemental analysis and IR, UV/vis, and 1H, 13C, and 2D NMR spectroscopy. An investigation into the chiroptical properties of these novel ruthenium bis(bipyridine) sulfoxide complexes has been carried out, and circular dichroism spectra are used to assign absolute stereochemistry. 相似文献
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Merrilactone A (1) has been shown to possess neurotrophic activity and thus is expected to hold therapeutic potential in the treatment of neurodegeneration diseases. In this paper, we report the total synthesis of (+/-)-1, employing, as key steps, a novel desymmetrization protocol of meso-diketone to construct the core cis-bicyclo[3.3.0]octyl system of 1 (3 --> 2) and a radical cyclization to install the highly congested C9-quaternary carbon (16 --> 17). 相似文献
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