- Boronic acid-catalyzed final-stage site-selective acylation for the total syntheses of O-3′-acyl bisabolol β-D-fucopyranoside natural products and their analogues
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The first concise total syntheses of O-3′-senecioyl α-bisabolol β-D-fucopyranoside (4a) and O-3′isovaleroyl α-bisabolol β-D-fucopyranoside (4b) were achieved through final-stage site-selective acylation via the activation of cis-vicinal diols by imidazole
- Nakamura, Yuki,Ochiai, Takayuki,Makino, Kazuishi,Shimada, Naoyuki
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p. 281 - 285
(2021/03/08)
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- Suppression of cytokine production by newly isolated flavonoids from pepper
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New flavonoid glycoside, kaempferol 3-O-α-[(6-P-coumaroyl galactopyranosyl-O-β-(→4)-O-α-rhamnopyranosyl-(1→4)]-O-α-rhamnopyranoside 1, in addition to five known flavonoid glycosides (2–6) kaempferol 3-O-[α-rhamnopyranosyl-(1→4)-O-α-rhamnopyranosyl-(1→6)-O]-β-galactopyranoside (kaempferol 3-O-β-isorhamninoside) 2, quercetin 3-O-[(2,3,4-triacetyl-α-rhamnopyranosyl)-(1 → 6)-β-galactopyranoside 3, quercetin 3-O-[(2,4-diacetyl-α-rhamnopyranosyl)-(1 → 6)]-3,4-diacetyl-β-galactopyranoside 4, quercetin 3-O-[(2,4-diacetyl-α-rhamnopyranosyl)-(1→6)]-2,4-diacetyl-β-galactopyranoside 5, quercetin 3-O-[(2,3,4-triacetyl-α-rhamnopyranosyl)-(1 → 6)-3-acetyl-β-galactopyranoside 6 were isolated from bell pepper (Capsicum annum L.) fruits and tested for both anti-inflammatory activity through cytokine production (TNF-α and IL-1β) and antioxidant activity through scavenging effect on 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay. Compounds 1–3 significantly suppressed production of TNF-α / IL-1β in cultured THP-1 cells previously co-stimulated by LPS in a dose-dependent manner (10.2/49.1, 28.1/55.7, and 35.2/57.5 μM respectively) whereas compounds 4–6 have relatively weaker inhibitory activity. (45.3/73.5, 48.2/65.6, and 42.2/67.4 μM respectively). All compounds 1–6 showed no cytotoxic activity against the growth of THP-1where the percentage of cell viability was (127.4, 108.5, 105.4, 103.9, 103.4, and 104.2 μM respectively). All isolated compounds exhibited higher radical scavenging activity than ascorbic acid in (DPPH) assay. These results indicated that bell pepper fruits could be an effective candidate for ameliorating inflammatory-associated complications.
- Allam, Ahmed E.
-
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- Sterically Hindered 2,4,6-Tri- tert-butylpyridinium Salts as Single Hydrogen Bond Donors for Highly Stereoselective Glycosylation Reactions of Glycals
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We demonstrate here that the strained and bulky protonated 2,4,6-tri-tert-butylpyridine salts serve as efficient catalysts for highly stereoselective glycosylations of various glycals. Moreover, the mechanism of action involves an interesting single hydrogen bond mediated protonation of glycals and not via the generally conceived Br?nsted acid pathway. The counteranions also play a role in the outcome of the reaction.
- Ghosh, Titli,Mukherji, Ananya,Kancharla, Pavan K.
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supporting information
p. 3490 - 3495
(2019/05/24)
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- Visible Light Enables Aerobic Iodine Catalyzed Glycosylation
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A versatile protocol for light induced catalytic activation of thioglycosides using iodine as an inexpensive and readily available photocatalyst was developed. Oxygen serves as a green and cost-efficient terminal oxidant and irradiation is performed with a common household LED-bulb. The scope of this glycosylation protocol was investigated in the synthesis of O-glycosides with yields up to 95 %.
- Krumb, Matthias,Lucas, Tobias,Opatz, Till
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supporting information
p. 4517 - 4521
(2019/08/06)
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- BIARYL AMIDES WITH MODIFIED SUGAR GROUPS FOR TREATMENT OF DISEASES ASSOCIATED WITH HEAT SHOCK PROTEIN PATHWAY
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Provided are biaryl amides and coumarin-based compounds with modified sugar groups for treatment of diseases associated with heat shock protein pathway. The compounds having the following formulas, wherein variables are as defined herein. Formulae (I), (II), (III), (IV), and (V), Pharmaceutical compositions of the compounds are also provided. These biaryl amides and coumarin-based derivatives with modified sugar groups are useful for treatment and prevention of diseases and disorders, including neurological disorders, such as neurodegenerative diseases and nerve damaging disorders, for example, diabetic peripheral neuropathy.
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Page/Page column 146; 180; 186-187
(2019/12/04)
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- Senescence tracers
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The instant invention relates to novel compounds useful for visualizing cell senescence, their preparation and use. In particular, this invention relates to novel fucose and amino-quinoline derivatives useful as senescence traces and their preparation.
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Page/Page column 11
(2018/01/05)
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- Isoquinoline-1-Carboxylate as a Traceless Leaving Group for Chelation-Assisted Glycosylation under Mild and Neutral Reaction Conditions
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Glycosyl isoquinoline-1-carboxylate was developed as a novel benchtop stable and readily available glycosyl donor. The glycosylation reaction was promoted by the inexpensive Cu(OTf)2 salt under mild reaction conditions. The copper isoquinoline-1-carboxylate salt was precipitated from the solution and thus rendered a traceless leaving group. Surprisingly, the proton from the acceptor was absorbed by the precipitated metal complex and the reaction mixture remained at neutral pH. The copper-promoted glycosylation was also proven to be completely orthogonal to the gold-promoted glycosylation, and an iterative synthesis of oligosaccharides from benchtop stable anomeric ester building blocks becomes possible under mild reaction conditions.
- Wang, Hao-Yuan,Simmons, Christopher J.,Blaszczyk, Stephanie A.,Balzer, Paul G.,Luo, Renshi,Duan, Xiyan,Tang, Weiping
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supporting information
p. 15698 - 15702
(2017/11/13)
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- Stereoselective Epimerizations of Glycosyl Thiols
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Glycosyl thiols are widely used in stereoselective S-glycoside synthesis. Their epimerization from 1,2-trans to 1,2-cis thiols (e.g., equatorial to axial epimerization in thioglucopyranose) was attained using TiCl4, while SnCl4 promoted their axial-to-equatorial epimerization. The method included application for stereoselective β-d-manno- and β-l-rhamnopyranosyl thiol formation. Complex formation explains the equatorial preference when using SnCl4, whereas TiCl4 can shift the equilibrium toward the 1,2-cis thiol via 1,3-oxathiolane formation.
- Doyle, Lisa M.,O'Sullivan, Shane,Di Salvo, Claudia,McKinney, Michelle,McArdle, Patrick,Murphy, Paul V.
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supporting information
p. 5802 - 5805
(2017/11/10)
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- Practical synthesis of latent disarmed S-2-(2-propylthio)benzyl glycosides for interrupted Pummerer reaction mediated glycosylation
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Practical synthetic methods to latent disarmed S-2-(2-propylthio)benzyl (SPTB) glycosides for interrupted Pummerer reaction mediated glycosylation have been discovered. Among them, both coupling reaction of PTB-Cl with glycosyl thiols and BF3·OEt2 promoted reaction of peracylated glycosides with PTB-SH produced peracylated SPTB glycosides in large scales and with high efficiency.
- Xu, Yang,Zhang, Qian,Xiao, Ying,Wu, Pinru,Chen, Wei,Song, Zejin,Xiao, Xiong,Meng, Lingkui,Zeng, Jing,Wan, Qian
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supporting information
p. 2381 - 2384
(2017/05/29)
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- Two new P-coumaroyl flavonoid glycosides having Cytokine increasing activity from Centaurium spicatum L
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Two new P-coumaroyl flavonol glycosides, Kaempferol 3-O-[β-D-glucopyranosyl- (1?→?4)-α-L-rhamnopyranosyl-(1?→?4)-α-L-rhamnopyranosyl-(1?→?6)-(4 trans- P-coumaroyl)]-β-D- galactopyranoside (1) and Quercetin 3-O-[β-D-glucopyranosyl-(1?→?4)-α-L-rhamnopyranos
- Allam, Ahmed E.,Nafady, Alaa M.,Hassanein, Ahmed M.M.,Mostafa, Mahmoud A.H.,El-Shanawany, Mohamed A.,Takano, Fumide,Ohta, Tomihisa
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p. 144 - 151
(2016/07/20)
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- Synthesis and evaluation of four hederagenin glycosides as α-glucosidase inhibitor
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The four hederagenin glycosides 1-4 were efficiently synthesized through one-pot sequential glycosylations with glycose 1-(trichloroacetimidate)s as donors, resulting in a significantly simplified synthetic procedure without isolation of glycosylation intermediates. The activity of the synthetic hederagenin glycosides 1-4 against α-glucosidase type IV was evaluated; hederagenin glycoside 4 containing an α-L-rhamnopyranosyl unit showed the best activity with an IC50 value of 47.9 μM. Copyright
- Liu, Qing-Chao,Guo, Tian-Tian,Guo, Shou-Dong,Li, Wen-Hong,Li, Dong
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p. 142 - 149
(2013/03/14)
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- Two new acetylated flavonoid glycosides from Centaurium spicatum L
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Two new acetylated flavonol glycosides, quercetin 3-O-[(2,4-diacetyl- α-L-rhamnopyranosyl)-(1→6)]- 2,4-diacetyl-β-D-galactopyranoside (1) and quercetin 3-O-[(2,4-diacetyl-α-L-rhamnopyranosyl)-(1→6)]-3,4- diacetyl-β-D-galactopyranoside (2), in addition to
- Allam, Ahmed E.,El-Shanawany, Mohamed A.,Backheet, Enaam Y.,Nafady, Alaa M.,Takano, Fumihide,Ohta, Tomihisa
-
experimental part
p. 388 - 393
(2012/08/29)
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- Studies on the conformational flexibility of α-l-rhamnose-containing oligosaccharides using 13C-site-specific labeling, NMR spectroscopy and molecular simulations: Implications for the three-dimensional structure of bacterial rhamnan polysaccha
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Bacterial polysaccharides are comprised of a variety of monosaccharides, l-rhamnose (6-deoxy-l-mannose) being one of them. This sugar is often part of α-(1 → 2)- and/or α-(1 → 3)-linkages and we have therefore studied the disaccharide α-l-Rhap-(1 → 2)-α-l
- Jonsson, K. Hanna M.,Saewen, Elin,Widmalm, Goeran
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experimental part
p. 2453 - 2463
(2012/04/23)
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- Unique phenyl ether type biflavonoids, zizyflavosides A and B with biomimetic synthesis for zizyflavoside A
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During our investigation of Zizyphus spina-christi (L.) Willd. leaves for anti-inflammatory activity, eight compounds were characterized. Two are new phenyl ether type biflavonoids, which were assigned as zizyflavosides A (1) and B (2). The structures of 1 and 2 were determined by spectroscopic analyses including 1D, 2D NMR and MS spectroscopic and chemical data. The other isolated compounds were known flavonoids kaempferol-3-O-rutinoside (5), quercetin-3-O-rutinoside (6), 3',5'-di-C-β-D-glucosylphloretine (7), quercetin-3-O-[β-D-xylosyl-(1→2)-α-L-rhamnoside] -4'-O-α-L-rhamnoside (8), epiafzelechin (9) and quercetin-3-O-[β-D- xylosyl-(1→2)-α-L-rhamnoside] (10). Zizyflavoside A was synthesized from quercetin-3-O-rutinoside and kaempferol-3-O-rutinoside using laccase as an enzyme and this biomimetic synthesis could be indication to its biosynthetic pathway. The Japan Institute of Heterocyclic Chemistry.
- Mostafa, Mahmoud,Takano, Fumihide,Ohta, Tomihisa
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p. 2497 - 2509
(2011/04/24)
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- 1,2-Trans-selective synthesis of glycosyl boranophosphates and their utility as building blocks for the synthesis of phosphodiester-linked disaccharides
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Figure Presented A highly 1,2-trans-selective synthesis of glycosyl boranophosphate derivatives by glycosylation of dimethyl boranophosphate with glycosyl iodides was developed. A study on the reaction mechanism indicated that the stereoselectivity of the
- Sato, Kazuki,Oka, Natsuhisa,Fujita, Shoichi,Matsumura, Fumiko,Wada, Takeshi
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experimental part
p. 2147 - 2156
(2010/06/17)
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- Improved synthesis of an ascaroside pheromone controlling dauer larva development in caenorhabditis elegans
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Using an efficient Wacker oxidation as a key step, we describe a significantly improved synthesis of the dauer-promoting ascaroside 2 for biological studies of the novel sterol ring methylase STRM-1.
- Martin, Rene,Schaefer, Tina,Theumer, Gabriele,Entchev, Eugeni V.,Kurzchalia, Teymuras V.,Knoelker, Hans-Joachim
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scheme or table
p. 3488 - 3492
(2010/03/02)
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- Total synthesis of ouabagenin and ouabain
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A full account of the total synthesis of ouabagenin and ouabain is described. A highly stereocontrolled anionic cycloaddition for the rapid construction of the basic steroid skeleton is a pivotal conversion for the whole strategy. A careful study was need
- Reddy, Maddi Sridhar,Zhang, Hongxing,Phoenix, Serge,Deslongchamps, Pierre
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supporting information; experimental part
p. 725 - 741
(2011/06/25)
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- Synthesis and cytotoxicity evaluation of natural α-bisabolol β-d-fucopyranoside and analogues
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α-Bisabolol β-d-fucopyranoside, a cytotoxic naturally occurring compound, was efficiently synthesized along with five other α-bisabolol glycosides (β-d-glucoside, β-d-galactoside, α-d-mannoside, β-d-xyloside and α-l-rhamnoside). Glycosidation of α-bisabol
- Piochon, Marianne,Legault, Jean,Gauthier, Charles,Pichette, Andre
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experimental part
p. 228 - 236
(2009/09/05)
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- Total synthesis of ouabagenin and ouabain
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(Chemical Equation Presented) The highly oxygenated steroid ouabagenin (1b) and its glycoside ouabain (1a) were prepared by a strategy based on a polyanionic cyclization. Starting building blocks A and B were combined to give the key intermediate C and transformed into 1b in 27 steps. Finally, ouabagenin (1b) was converted into ouabain (1a) in six steps (see scheme).
- Zhang, Hongxing,Sridhar Reddy, Maddi,Phoenix, Serge,Deslongchamps, Pierre
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p. 1272 - 1275
(2008/12/22)
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- TRITERPENES DERIVATIVES AND USES THEREOF AS ANTITUMOR AGENTS OR ANTI-INFLAMMATORY AGENTS
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A compound of formula (1): wherein R1 is selected from the group consisting of H, α-L-Rhamnopyranose, α-D-Mannopyranose, β-D-Xylopyranose, β-D-Glucopyranose, and α-D-Arabinopyranose; R2 is selected from CH3, COOH, CH2OH, COOCH3 and CH2O-α-D-Arabinopyranose; with the proviso that the compound of formula (I) is not a compound of formula (I) wherein R1 is β-D-Glucopyranose and R2 is COOH; wherein R1 is α-L-Rhamnopyranose and R2 is CH3; wherein R1 is β-D-Glucopyranose and R2 is CH2OH; wherein R1 is β-D-Xylopyranose and R2 is CH2OH; wherein R1 is α-L-Rhamnopyranose and R2 is COOCH3, wherein R1 is H and R2 is CH3; wherein R1 is H and R2 is CH2OH; wherein R1 is H and R2 is COOH; or wherein R1 is H and R2 is COOCH3, or a pharmaceutically acceptable salt thereof.
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Page/Page column 13
(2008/12/06)
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- Antioxidant C-glycosyl flavones from the leaves of Sasa kurilensis var. gigantea
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C-glycosyl flavones, kurilensin A (1) and B (2), together with two known compounds, tricin-4′-O-β-d-glucopyranoside (3) and tricin-5-O-β-d-glucopyranoside (4), were isolated from hot-water extracts of the leaves of Sasa kurilensis. The structure of the compounds was determined by spectroscopic analyses including 1D, 2D NMR and MS. The absolute configuration of sugar moieties in 1 and 2 was determined by chiral HPLC analyses of the benzoyl derivatives of acid hydrolysis. Compounds 1 and 2 exhibited higher radical scavenging activity than ascorbic acid in the 1,1-diphenyl-2-pycrylhydrazyl (DPPH) assay system.
- Hasegawa, Tatsuya,Tanaka, Ayumi,Hosoda, Akiko,Takano, Fumihide,Ohta, Tomihisa
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p. 1419 - 1424
(2008/09/20)
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- Glycosidation of lupane-type triterpenoids as potent in vitro cytotoxic agents
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The weak hydrosolubility of betulinic acid (3) hampers the clinical development of this natural anticancer agent. In order to circumvent this problem and to enhance the pharmacological properties of betulinic acid (3) and the lupane-type triterpenes lupeol (1), betulin (2), and methyl betulinate (7), glycosides (β-d-glucosides, α-l-rhamnosides, and α-d-arabinosides) were synthesized and in vitro tested for cytotoxicity against three cancerous (A-549, DLD-1, and B16-F1) and one healthy (WS1) cell lines. The addition of a sugar moiety at the C-3 or C-28 position of betulin (2) resulted in a loss of cytotoxicity. In contrast, the 3-O-β-d-glucosidation of lupeol (1) improved the activity by 7- to 12-fold (IC50 14-15.0 μM). Moreover, the results showed that cancer cell lines are 8- to 12-fold more sensitive to the 3-O-α-l-rhamnopyranoside derivative of betulinic acid (IC50 2.6-3.9 μM, 22) than the healthy cells (IC50 31 μM). Thus, this study indicates that 3-O-glycosides of lupane-type triterpenoids represent an interesting class of potent in vitro cytotoxic agents.
- Gauthier, Charles,Legault, Jean,Lebrun, Maxime,Dufour, Philippe,Pichette, Andre
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p. 6713 - 6725
(2007/10/03)
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- 6R-(3,6-DIDEOXY-L-ARABINO-HEXOPYRANOSYLOXY)HEPTANOIC ACID, PREPARATION PROCESS FOR THE SAME AND DAUER EFFECT THEREOF
-
The present invention relates to a determination of a stereochemistry, a synthesis and dauer effect of 6R-(3,6-dideoxy-L-arabino-hexopyranosyloxy) heptanoic acid as a pheromone isolated from the Caenorhabditis elegance related to suppress of aging and
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Page/Page column 5; 10
(2008/06/13)
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- Large-scale synthesis of β-L-fucopyranosyl phosphate and the preparation of GDP-β-L-fucose
-
A practical 15-mmol large-scale synthesis of β-L-fucopyranosyl dicyclohexylammonium phosphate from L-fucose in 63percent overall yield was developed.The synthesis took advantage of a neighboring Bz-2 group participating in a Koenigs-Knorr like glycosylati
- Adelhorst, Kim,Whitesides, George M.
-
-