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911.
A complete reversal of diastereoselectivity was observed for reactions of the trifluoroacetaldehyde ethyl hemiacetal with enamines and imines, derived from propiophenones, that produce 4,4,4-trifluoro-1-aryl-3-hydroxy-2-methyl-1-butanones. This process serves as the first reliable, metal-free, complementary anti- and syn-selective method to prepare 4,4,4-trifluoro-1-aryl-3-hydroxy-2-methyl-1-butanones.  相似文献   
912.
New Lycopodium alkaloids, lyconadins C (1) and F (2), were isolated from the club moss Lycopodium complanatum. Lyconadin C (1) is a new C16N2-type Lycopodium alkaloid possessing unique fused-tetracyclic ring system consisting of a cycloheptene ring fused to a decahydroquinoline and pyridone rings. Lyconadin F (2) possesses a primary amide moiety in its molecular, which is the first example of Lycopodium alkaloids. Biogenetically, lyconadins C (1) and F (2) might be related to lyconadins A (4) and B (5). The structures and relative stereochemistry of 1 and 2 were elucidated on the basis of spectroscopic data. The absolute stereochemistry of 2 was elucidated by chemical correlations with lyconadin B (5) through hemiaminal form of lyconadin F (3).  相似文献   
913.
Chemical synthesis of pseudaminic acid is described. Starting from N-acetylglucosamine, deoxygenation and deoxyamination with stereo-inversion afforded 6-deoxy-AltdiNAc, which is the key intermediate for the biosynthesis of pseudaminic acid. Subsequently, the elongation reaction via In-mediated allylation of 6-deoxy-AltdiNAc with bromomethacrylate ester derivative followed by ozonolysis and hydrolysis gave the desired pseudaminic acid. Furthermore, we demonstrated glycosylation with dibenzyl phosphite derivative of pseudaminic acid as the glycosyl donor to afford disaccharide.  相似文献   
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918.
The synthesis of bioactive oligosaccharides is too tedious to scale up for commercialization. However, structurally simplified glycomimetics are commercializable, if they can be synthesized much more easily than the oligosaccharides while having a comparable bioactivity. In this study, we propose a 2-oxabutane (OB) structure as an imitation of the internal monosaccharide units in oligosaccharides. Two trimannoside and three pentamannoside OB-glycomimics were synthesized in remarkably short steps. Among them, Manα1-OB-2Man 10, a trimannoside mimic, showed eight-fold affinity toward concanavalin A (ConA) relative to methyl mannoside in latex agglutination lectin assay and equilibrium dialysis assay (EDA), while the other mimics showed three- to four-fold affinities. EDA indicated that the bindings between each mimic molecule and a ConA subsite were all in one-to-one stoichiometry and thus these mimics were monovalent ligands, excluding multivalence effect for the high affinities. The strong affinity of 10 could be explained by the occupation of two mannose binding sites of a ConA subsite by its two mannose units. Mimic 10 proved to be even a better ligand for ConA than the natural disaccharide Manα1,2Man, while been much more easy to synthesize, thereby illustrating the potential of the approach here presented.  相似文献   
919.
Amphiphilic pincer palladium complexes bearing hydrophilic and hydrophobic side chains on the planar NCN palladium pincer backbone were designed and prepared via the ligand introduction route. The complexes self-assembled under aqueous conditions to form vesicles with bilayer membranes containing palladium species. The catalytic activity of the vesicles in the Miyaura-Michael reaction in water was investigated.  相似文献   
920.
An important characteristic of n-alkanes and fatty acids is the great diversity of solid-state structures, which we can hardly imagine from their simple molecular structures. The variety of crystalline states can be categorized with two concepts: polymorphism and polytypism. Polytypism refers to higher-order structural variation caused solely by the stacking mode of molecular layers. Two basic polytypic structures, single-layer and double-layer, were confirmed in several modifications of n-alkanes and fatty acids having an O⊥ subcell. During the last decade, the two basic polytypes of n-alkanes have been intensively studied mainly by vibrational spectroscopy, with a focus on their formation conditions, thermodynamic stability, and molecular motions. This review summarizes new progress in the context of research on the polytypism of long-chain compounds.  相似文献   
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