- Α - galactose ceramide new isomer and its synthetic method
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The invention provides an alpha-galactosyl ceramide new isomer and its synthetic method. Configuration of sphingosine chain is changed to 4,5-cis double bond sphingosine chain. According to the invention, reaction steps are shortened, yield is raised, and aftertreatment and purification steps are omitted. The synthetic method can be used for total synthesis of similar glycosyl ceramide and satisfies wide range of development, research and application of different glycosyl ceramide.
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Paragraph 0030; 0031
(2017/10/31)
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- The convergent total synthesis of cytotoxic homospisulosine and its 3-epi-analogue
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A common strategy for the total synthesis of cytotoxic homospisulosine 7 and its 3-epi-analogue 10 was achieved in a stereoconvergent manner, from 3,5-di-O-benzyl-d-xylofuranose with the efficient use of rearranged products 14-17. The key transformations of this approach are [3,3]-heterosigmatropic rearrangements of allylic substrates 18 and 19 to establish a stereogenic amino group and regioselective intramolecular cyclization to form common oxazolidinones 28 and 29. Elongation of the side chain was accomplished via a Wittig reaction. Several compounds were evaluated for their in vitro antiproliferative/cytotoxic activity by the MTT method employing five different human cancer cell lines (Jurkat, MDA-MB-231, MCF-7, HCT-116 and Caco-2). The obtained data revealed that homospisulosine 7 exhibited the most significant inhibitory effects among all of the screened compounds on the panel of the tested cell lines with IC50 values comparable to those of conventional anticancer agents such as cisplatin and etoposide.
- Stanková, Kvetoslava,Martinková, Miroslava,Gonda, Jozef,Bago, Martina,Pilátová, Martina,G?nciová, Gabriela
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p. 1394 - 1407
(2015/12/09)
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- Synthesis and inhibitory activities against colon cancer cell growth and proteasome of alkylresorcinols
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We have identified alkylresorcinols (ARs) as the major active components in wheat bran against human colon cancer cell growth (HCT-116 and HT-29) using a bioassay-guided approach. To further study the structure-activity relationships, 15 ARs and their intermediates (1-15) were synthesized expediently by the modified Wittig reaction in aqueous media, and six 5-alkylpyrogallols and their analogues (16-21) were prepared by the general Grignard reaction. The synthetic AR analogues were evaluated for activities against the growth of human colon cancer cells HCT-116 and HT-29 and the chymotrypsin-like activity of the human 20S proteasome. Our results found that (1) AR C13:0 and C15:0 (13 and 14) had the greatest inhibitory effects in human colon cancer cells HCT-116 and HT-29, while decreasing or increasing the side chain lengths diminished the activities; (2) two free meta-hydroxyl groups at C-1 and C-3 on the aromatic ring of the AR analogues greatly contributed to their antitumor activity; (3) the introduction of a third hydroxyl group at C-2 (20 and 21) into the aromatic ring of the AR analogues yielded no significant enhancement in activity against HCT-116 cells and decimated the effects against HT-29 cells, but dramatically increased the activity against the chymotrypsin-like activity of the human 20S proteasome; and (4) AR C11:0 (12) was found to have the greatest effect in a series of AR C9:0-C17:0 against the chymotrypsin-like activity of the human 20S proteasome.
- Zhu, Yingdong,Soroka, Dominique N.,Sang, Shengmin
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p. 8624 - 8631
(2012/11/13)
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- Stereoselective synthesis of N,O,O,O-tetraacetyl-D-ribo-phytosphingosine, N,O,O-triacetyl-D-erythro-sphingosine and N,O,O-triacetyl sphingonine from a common chiral intermediate derived from D-mannitol
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An efficient protocol for the stereoselective synthesis of tetraacetyl-D-ribo-hytosphingosine, triacetyl-D-erythro-sphingosine and triacetyl sphinganine has been devised from a common chiral intermediate derived from commercially available D-mannitol. The key steps involved are Sharpless epoxidation, Miyashita C(2) selective endo mode azide opening of 2,3-epoxy alcohol, and selective E-Wittig olefination. ARKAT-USA, Inc.
- Mettu, Ravinder,Thatikonda, Narendar Reddy,Olusegun, Oladoye Sunday,Vishvakarma, Ramesh,Vaidya, Jayathirtha Rao
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p. 421 - 436
(2013/11/06)
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- α-glycosphingolipids via chelation-induced anomerization of O- And s-glucuronic and galacturonic acid derivatives
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Bacterial glycolipids containing either α-glucuronic acid or α-galacturonic acid residues have an important role in the innate-type immune response to Gram-negative bacteria. Synthesis of closely related compounds, including a novel α-SO2 glycolipid mimetic, is described from carbohydrate precursors where anomerization is a key step. Very high stereoselectivites (>97:3 in favor of α) were observed from O-glycoside precursors.
- Pilgrim, Wayne,Murphy, Paul V.
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supporting information; experimental part
p. 939 - 942
(2009/09/08)
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- An expedient synthesis of 5-n-alkylresorcinols and novel 5-n-alkylresorcinol haptens
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The first synthesis of bioactive long alkyl chain 5-n-alkylresorcinols, present in whole grain products, by a novel modification of the Wittig reaction is described. All the main long chain 5-n-alkylresorcinols present in rye and wheat, including C23 and C25 analogues and haptens, which have not been previously prepared, were synthesised. Microwave-promoted reactions of a semistabilized ylid and alkanals in water gave good yields in both pressurized and open systems. An alternative microwave-promoted synthesis starting from non-stabilized alkyltriphenylphosphonium salts and 3,5-dimethoxybenzaldehyde worked as well. Aqueous media were suitable for the reactions even if the starting materials were not soluble in water. The 5-n-alkylresorcinols are potential biomarkers of whole grain intake, and the new hapten derivatives of 5-n-alkylresorcinols will open the way for the immunochemical detection techniques of alkylresorcinols.
- Parikka, Kirsti,Waehaelae, Kristiina
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supporting information; experimental part
(2010/04/22)
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- GLYCOLIPIDS AND ANALOGUES THEREOF AS ANTIGENS FOR NK T CELLS
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This invention relates to immunogenic compounds which may serve as ligands for NKT (natural killer T) cells and to methods of use thereof in modulating immune responses.
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Page/Page column 83; 84
(2008/06/13)
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- The total syntheses of D-erythro-sphingosine, N-palmitoylsphingosine (ceramide), and glucosylceramide (cerebroside) via an azidosphingosine analog
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The total synthesis of D-erythro-sphingosine (9) was performed by a chirospecific method starting from D-galactose via an azidosphingosine intermediate to give highly homogeneous ( > 99.9% C18:1) sphingosine base (9) which contained no observable olefin isomerization by product and was demonstrated to be optically pure by a novel method utilizing Mosher's acid. Ceramide (10) was prepared from this sphingosine (9) with highly homogeneous (99.8% C16:0) palmitic acid by two methods. The cerebroside glucosylceramide (23) was the next sphingolipid in this series to be synthesized in a highly homogeneous form. These three sphingolipids are currently being used for biophysical studies of the structures of their hydrated bio-molecular assemblies.
- Duclos Jr., Richard I
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p. 111 - 138
(2007/10/03)
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- Close-range attraction in Lygocoris pabulinus (L.)
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Males of the green capsid bug, Lygocoris pabulinus, exhibit a specific courtship behavior, i.e., a vibration of the abdomen. When both live and dead females were offered to males, this vibration behavior was elicited in most of the males tested. When females were dissected into separate body parts, heads, wings, and legs elicited equal responses, while thorax plus abdomen elicited a much lower response. When separate body parts were extracted, the leg extracts elicited significantly stronger responses than any other extract. This suggests that female L. pabulinus legs are either the source of a close-range sex pheromone or that pheromone is accumulated on the legs due to grooming behavior. The leg extracts contained several hydrocarbons such as n-alkenes, n-alkanes, and some methylalkanes. Female extracts contained more (Z)-9-pentacosene and male extracts contained more (Z)-9-heptacosene. Substrates on which females had walked elicited similar responses as female legs, indicating that the pheromone is deposited on the substrate. This enlarges the functional range of low-volatility compounds, which are thought to function only when sexes are in close vicinity or in contact.
- Drijfhout, Falko P.,Groot, Astrid T.
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p. 1133 - 1149
(2007/10/03)
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- Synthesis and biological activity of new diarylalkenes
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Condensation of 5-nitro-, 3-chloro-, and 5-chlorosalicylic acid with formaldehyde afforded dimeric disalicylmethanes which were O-methylated with dimethyl sulfate and oxidized with chromium(VI) oxide to give the diarylketones 10, 11, 12. Wittig reaction with ylides obtained by deprotonation of alkyltriphenylphosphonium salts with sodium bis (trimethylsilyl)amide yielded a series of diarylalkenes. Some of the obtained compounds showed high antimicrobial activity in vitro against Bacillus subtilis and Mycobacterium smegmatis.
- Golebiewski, W. Marek,Cieniecka-Ros?onkiewicz,Szybinska
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- Novel antifeedant and insecticidal compounds from avocado idioblast cell oil
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Several insecticidal compounds have been identified by bioassaydriven fractionation of avocado, Persea americana Mill, idioblast cell oil. A flash chromatography fraction of the oil showed substantial toxicity to early instars of the generalist insect herbivore, Spodoptera exigua (Hubner) (100% mortality after seven days). Following further fractionation, five biologically active compounds, 2-(pentadecyl)furan, 2-(heptadecyl)furan, 2-(1E-pentadecenyl)furan, 2-(8Z, 11Z-heptadecadienyl)furan, and the triglyceride triolein, were identified. Several minor components were also tentatively identified, including 2-(1Z-pentadecenyl)furan, 2-(1E-heptadecenyl)furan, and 2-(1E,8Z, 11Z-heptadecatrienyl)furan. Several 2-alkylfurans of this type have been reported previously from avocado (Persea spp.) and have received the common name of avocadofurans. The major compounds were tested individually for toxic and growth inhibitory effects. Individually, the compounds had low to moderate toxicity. Of these, 2-(pentadecyl)furan had the greatest effects, with an LC50 value of 1031 μg/g. At concentrations of 600 μg/g or higher in diets, larval growth was inhibited by >70% compared to controls. The analogous 2-(heptadecyl)furan had an LC50 value of 1206 μg/g, and also significantly reduced larval growth (>75% versus controls) at concentrations of > 600 μg/g. The unsaturated analogs 2-(1E-pentadecenyl)furan and 2-(8Z, 11Z-heptadecadienyl)furan were less toxic. Triolein was only weakly toxic, with an LC50 value of 10,364 μg/g diet. Larval growth was inhibited only at concentrations of 7000 μg/g or higher. The potential of avocadofurans in insect control is discussed.
- Rodriguez-Saona, Cesar,Millar, Jocelyn G.,Maynard, David F.,Trumble, John T.
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p. 867 - 889
(2007/10/03)
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- Improved, gram scale synthesis of N,O,O-triacetyl-erythro- and threo-C18-sphingosines from serine
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A formal total synthesis of all four (E)C18-sphingosine stereoisomers from serine has been carried out. This involves the thiazole-based homologation of the amino acid into a chiral 3-amino-2,4-dihydroxybutanal 1 and the Wittig olefination of 1 with the ylide from the C14 alkyl phosphonium salt 2. The photoisomerization of the resulting mixture of Z- and E-alkenes affords the target sphingosine. Thus, N,O,O-triacetyl-D-erythro C18-sphingosine 5 and the L-threo isomer 10 were prepared in 43-44% overall yield from the aldehyde (S,S)-1a and (2R,3S)-1b, respectively. The corresponding antipodal L-erythro and D-threo isomers can be prepared in the same way starting from aldehydes ent-1a and ent-1b, respectively. Conversion of the above acetyl sphingosines into the free sphingoid bases has been reported in the literature.
- Dondoni, Alessandro,Perrone, Daniela,Turturici, Elisa
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p. 2389 - 2393
(2007/10/03)
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- Asymmetric synthesis of solenopsins A, B and C
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Solenopsins A, B and C have been synthesized in enantiomerically pure forms from the corresponding anti-1,5-diols which have been obtained from glutaric anhydride by an asymmetric synthesis induced by chiral sulfoxides.
- Solladie, Guy,Huser, Nathalie
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p. 153 - 156
(2007/10/02)
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- Structure-activity relationship of α-galactosylceramides against b16- bearing mice
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Agelasphin-9b, (2S,3S,4R)-1-O-(α-D-galactopyranosyl)-16-methyl-2-[N- ((R)-2-hydroxytetracosanoyl)-amino]-1,3,4-heptadecanetriol, is a potent antitumor agent isolated from the marine sponge Agelas mauritianus. Various analogues of agelasphin-9b (a lead compound) were synthesized, and the relationship between their structures and biological activities was examined using several assay systems. From the results, KRN7000, (2S,3S,4R)-1-O-(α- D-galactopyranosyl)-2-(N-hexacosanoylamino)-1,3,4-octadecanetriol, was selected as a candidate for clinical application.
- Morita,Motoki,Akimoto,Natori,Sakai,Sawa,Yamaji,Koezuka,Kobayashi,Fukushima
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p. 2176 - 2187
(2007/10/02)
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- Enantiospecific Synthesis of Sphingosine and Ceramide Stereoisomers with 3S Configuration from D-Glucose
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Utilizing the carbon framework (C3-C6) and chirality (at C4 and C5) of D-glucose, (2S,3S,4E and 2R,3S,4E)-2-amino-4-octadecene-1,3-diol (sphingosine analogues) and four stereoisomers (2S,3S,4E-,2S,3S,4Z-,2R,3S,4E-,and 2R,3S,4Z-) of the ceramide derivatives were synthesized in a stereocontrolled way.
- Fujita, Shuji,Sugimoto, Mamoru,Tomita, Kenkichi,Nakahara, Yoshiaki,Ogawa, Tomoya
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p. 2561 - 2570
(2007/10/02)
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- A CONVENIENT SYNTHESIS OF LONG-CHAIN 3-n-ALKYLTHIOPHENES AND 3-n-ALKYLFURANS
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The syntheses of 3-substituted long-chain furans and thiophenes by a Wittig reaction are described. 1H-NMR and UV data of these compounds are reported.
- Shabana, R.,Amer, Adel,Mark, H. B.,Zimmer, Hans
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p. 299 - 306
(2007/10/02)
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- A NOVEL ROUTE TO D-erythro-SPHINGOSINE AND RELATED COMPOUNDS FROM MONO-O-ISOPROPYLIDENE-D-XYLOSE OR -D-GALACTOSE
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An efficient synthesis of D-erythro-sphingosine and -ceramide from D-xylose or D-galactose is described.A mixture of 2,4-O-isopropylidene-D-threose and its formate, which is available in one step from 3,5-O-isopropylidene-D-xylofuranose or 4,6-O-isopropylidene-D-galactopyranose, was subjected to the Wittig alkenation with triphenylphosphonio-tetra- and -hexa-decylid.The resulting 1,3-O-isopropylidenated C18 and C20 alkenes were each transformed, by introduction of an azido group at C-2, and selective reduction of the azide, into the corresponding 1,3-O-protected sphingosines that have the 2(S),3(R)-D-erythro configuration, from which a variety of ceramides were prepared by the sequence of N-acylation with the stearoyl or lignoceroyl group, and hydrolytic removal of the isopropylidene group.Some ceramides were also obtained by direct N-acylations of the corresponding sphingosines.
- Kiso, Makoto,Nakamura, Akemi,Tomita, Yoshimi,Hasegawa, Akira
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p. 101 - 112
(2007/10/02)
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