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71.
Substituted 2′-hydroxyacetophenone 4-bromophenylhydrazones are oxygenated readily in the presence of Co(Salpr) in ethanol to give 2-(4-bromophenylazo)-1,3-benzodioxoles in good yield. The results are rationalized in terms of the decomposition of a peroxy cobalt(III) complex intermediate by a mechanism similar to the Darkin oxidation. 相似文献
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73.
Yoshihiko Ito Hiroshi Imai Takaharu Matsuura Takeo Saegusa 《Tetrahedron letters》1984,25(29):3091-3094
This paper describes the finding that BF3 etherate effectuates the conjugate additions of copper(I) aldimines, generated in situ from lithium aldimines and Cu(I) halide, to α,β-unsaturated carbonyl compounds to produce 4-(N-alkylimino)-ketones, which give on acid hydrolysis 1,4-diketone derivatives. 相似文献
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76.
Akira Hasegawa Takao Nagahama Hitoshi Ohki Kenji Hotta Hideharu Ishida Makoto Kiso 《Journal of carbohydrate chemistry》2013,32(3):493-498
Development of an efficient α-glycoside synthesis of sialic acids is critically significant for the syntheses of sialoglycoconjugates, especially gangliosides which carry important biological functions1 in biological systems. Previously, we demonstrated2 a new α-glycosylation of sialic acids by use of dimethyl(methylthio)sulfonium triflate (DMTST)3 as the glycosyl promoter, the suitably protected glycosyl acceptors and the methyl 2-thioglycoside 1 of N-acetylneuraminic acid (Neu5Ac) as the donor in acetonitrile under kinetically controlled conditions, and accomplished4 the syntheses of a variety of gangliosides and their analogs. 相似文献
77.
Yukihiro Isogai Hideharu Ishida Makoto Kiso Akira Hasegawa 《Journal of carbohydrate chemistry》2013,32(9):1119-1137
ABSTRACT 3-O-Sulfo glucuronyl neolactohexanosyl ceramide derivatives (heptasaccharides) have been synthesized. Condensation of 2-(trimethylsilyl)ethyl 2,4,6-tri-O-benzyl-β-D-galactopyranoside (2) with 4-O-acetyl-3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl trichloroacetimidate (1) gave the desired β-glycoside 3, which was converted into 2-(trimethylsilyl)ethyl O-(2-acetamido-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranosyl)-(1→3)-2,4,6-tri-O-benzyl-β-D-galactopyranoside (4) via removal of the O-acetyl and N-phthaloyl groups, followed by N-acetylation. Glycosylation of 4 with O-(methyl 4-O-acetyl-2-O-benzoyl-3-O-levulinoyl-β-D-glucopyranosyluronate)-(1→3)-2,4,6-tri-O-benzoyl-α-D-galactopyranosyl trichloroacetimidate (5) using trimethylsilyl trifluoromethanesulfonate gave the target tetrasaccharide 6, which was transformed via removal of the benzyl group, O-benzoylation, removal of the 2-(trimethylsilyl)ethyl group and imidate formation into the tetrasaccharide donor 9. Glycosylation of 2-(trimethylsilyl)ethyl O-(2-acetamido-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranosyl)-(1→3)-O-(2,4,6-tri-O-benzyl-β-D-galactopyranosyl)-(1→4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside (10) with the imidate donor 9 using trimethylsilyl trifluoromethanesulfonate gave the desired heptasaccharide 11, which was transformed into the heptasaccharide imidate donor 14. Glycosylation of (2S, 3R, 4E)-2-azido-3-O-benzoyl-4-octadecene-1,3-diol (15) with 14 gave β-glycoside 16, which was transformed into the four target compounds, via reduction of the azido group, coupling with octadecanoic acid or tetracosanoic acid, selective removal of the levulinoyl group, O-sulfation, hydrolysis of the methyl ester group and O-deacylation. 相似文献
78.
Takashi Nakanishi Masanobu Naito Yukikazu Takeoka Kazunori Matsuura 《Current Opinion in Colloid & Interface Science》2011,16(6):482-490
In this review article, we describe recent progress about exotic self-assembled systems with various dimensions including biomolecules, supramolecules, unique hydrophobic amphiphiles, polymers, nano-clusters, and colloidal particles. Construction of robust biomolecular assemblies with exotic structures, such as ring and hollow capsule, is achieved by rational designs of symmetric biomolecular conjugates. In addition, we comprehensively summarized leading-edge topics on optical/topological properties of self-assembled hybrid systems, such as circularly polarized luminescence or structural color. The preparation of colloidal amorphous array with photonic band gap-induced angle-independent structural color is also achieved in consideration of the following situations: i) two-body sphere–sphere potential, ii) disorder packing using different sizes of colloidal particles, and iii) softness of colloidal particles. Lastly, we demonstrated useful utilizations of exotic self-assembled objects. Flakelike microparticles were transcribed into various nano-flake metals and applied as temperature indicator for the local heating of an addictive. All findings described here show meaningful hybrid strategies in self-assembly techniques and their functionalization as well as materialization. 相似文献
79.
Polysialoglycoconjugates, such as polysialylated ganglio-series gangliosides and N-CAM (neural cell adhesion molecule), are of interest because of their important physiological functions in association with neural cell development, differentiation, neuron network formation, and so on.2-4 Chemical synthesis of these glycoconjugates provides an effective method to elucidate their biological significance in nature at the molecular level, providing not only genuine original glycoconjugates but also their derivatives and analogs designed for biological investigation. We have established5 an efficient method to construct dimeric and trimeric sialoglycosides by using the lactonated sialic acid derivatives as building blocks, and succeeded in the systematic synthesis of various polysialogangliosides such as GD3, GQ1b, GQlbα and, very recently, GT3.6 In this paper, as a part of our continuous synthetic approach directed toward the polysialoglycoconjugates, we report the first synthesis of α-linked tetrameric sialoglycosides coupled with a galactose and lactose residue. 相似文献
80.
Akihiko Kameyama Hideharu Ishida Makoto Kiso Akira Hasegawa 《Journal of carbohydrate chemistry》2013,32(4):549-560
ABSTRACT The first total synthesis of tumor-associated glycolipid antigen, sialyl Lewis X is described. Glycosylation of 2-(trimethylsilyl)ethyl O-(2-acetamido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranosyl)-(1→3)-O-(2,4,6-tri-O-benzyl-β-D-galactopyranosyl)-(1→4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside (1) with methyl 2,3,4-tri-O-benzyl-1-thio-β-L-fuco-pyranoside (4) gave the α-glycoside (5), which was converted by reductive ring-opening of the benzylidene acetal into the glycosyl acceptor (6). Dimethyl(methylthio)sulfonium triflate-promoted coupling of 6 with methyl O-(methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylonate)-(2→3)-2,4,6-tri-O-benzoyl-1-thio-β-D-galactopyranoside (7) afforded the desired hexasaccharide 8 in good yield. Compound 8 was converted into the α-trichloroacetimidate 11, via reductive removal of the benzyl groups, O-acetylation, removal of the 2-(trimethylsilyl)ethyl group, and treatment with trichloroacetonitrile, which, on coupling with (2S, 3R, 4E)-2-azido-3-O-benzoyl-4-octa-decene-1,3-diol (12), gave the β-glycoside 13. Finally, 13 was transformed, via selective reduction of the azide group, condensation with octadecanoic acid, O-deacylation, and hydrolysis of the methyl ester group, into the title compound 16. 相似文献