Electrosyntheses of disaccharides from phenyl or ethyl 1-thioglycosides

Constant current electrolyses of the glycosyl donors phenyl and ethyl 2,3,4,6-tetra-O-benzyl-1-thio-β-d-glycopyranoside in dry acetonitrile in the presence of various primary and secondary sugar alcohols, performed in an undivided cell, gave β-linked disaccharide derivatives selectively in good yields. Phenyl 2,3,4,6-tetra-O-benzoyl-1-thio-β-d-glycopyranoside gave the β-glucosides exclusively in good to moderate yields.     

Catalytic ceric ammonium nitrate mediated synthesis of 2-deoxy-1-thioglycosides

Synthesis of 2-deoxy-1-thioglycosides from glycals, mediated by catalytic amounts of ceric ammonium nitrate is reported. Apart from the 2-deoxy-1-thioglycosides, formation of the 2,3-unsaturated enose, corresponding to the Ferrier product, is also observed, especially for the glucal substrates. A radical oxocarbenium ion and a thiolate intermediates are most likely to mediate the reaction. Upon synthesis of 2-deoxy-1-thioglycosides, few representative glycosylation reactions with both aglycosyl and glycosyl acceptors were performed and alpha-anomeric 2-deoxy glycosides were obtained exclusively.     

Synthesis of aryl-2-deoxy-D-lyxo/arabino-hexopyranosides from 2-deoxy-1-thioglycosides

The synthesis of either anomers of aryl 2-deoxy-D-glycopyranosides from 2-deoxy-1-thioglycosides is reported. The alpha-anomers form as the major product when thioglycosides react with differently substituted phenols and naphthols, in the presence of N-iodosuccinimide/triflic acid. On the other hand, reaction of the thioglycosides with bromine initially, followed by reaction with aryloxy anions lead to aryl 2-deoxy-beta-D-glycosides with high specificities.     

5-Amino-2-pyridyl 1-thioglycosides in synthesis of analogs of glycosyltransferases substrates

We present the synthesis of 1-thioglycosyl derivatives of uridine, which were designed to act as potential donor substrates for glycosyltransferases. We constructed such analogs using 5-amino-2-pyridyl 1-thioglycosides as glycosyl units which were connected to uridine via succinic linker. For preparation of the amide bonds we applied different condensation procedures.     

Separation of anomeric aryl glycosides and 1-thioglycosides by chromatography on a cation-exchange resin

Calculations of the electronic distribution in α- and β-D-glucopyranose, β-D-arabinopyranose, and 2-deoxy-β-D-erythro-pentopyranose, as well as in the enediol form of D-erythro-pentulose and its dianion, have been performed by the CNDO/2 method, taking into account the exact geometry of the molecules. The results obtained are discussed in relation to the anomeric effect, dipole moment, ionization constants, and reactivity of the various sugars. The dipole moment of methyl α-D-glucopyranoside was also determined.     

Highly efficient synthesis of 1-thioglycosides in solution and solid phase using iminophosphorane bases

Disaccharides of 1-thioglycosides, an important class of glycomimics, can be synthesized by direct S-alkylation in exceptionally high yields when iminophosphorane bases are employed. The reaction conditions employed appear to be general and stereospecific. Axial and equatorial 4-triflates and primary tosylates of alkyl pyranosides provided excellent yields of thio-disaccharides without substantial elimination products. The iminophosphorane bases also proved to be useful in solid support-bound couplings of thioglycosides though with lower efficiency.     

Synthesis and biological evaluation of 5-fatty-acylamido-1, 3, 4-thiadiazole-2-thioglycosides

In the present study, the synthesis of 1, 3, 4-thiadiazole-based thioglycosides were accomplished in good yields with employing a convergent synthetic route. The starting material 5-amino-1, 3, 4-thiadiazole-2-thiol and followed by a series of 5-fatty-acylamido-1, 3, 4-thiadiazole-2-thiols (4a–4j) were synthesized with different fatty acid chlorides. The glycosylation of compounds 4a–4j were achieved with trichloroacetimidate methodology. Antimicrobial and cytotoxicity activities of title compounds were evaluated. Among the entire compounds lauric acid and myristic acid derivatives showed good and moderate antimicrobial activity. In case of cytotoxicity results of compounds 8a–8j and 9a–9j, the acetate protected short chain (C6:0, C8:0, C10:0) compounds and the free hydroxyl long chain saturated (C16:0, C18:0) and unsaturated (C18:1, C22:1) compounds exhibited good activity against different cancer cell lines. Further, the free hydroxyl compounds 9a, 9c–9j did not show any toxicity towards normal CHO-K1 cell line whereas acylated compounds 8a–8j exhibited toxicity.     

Preparation of anomeric pairs of 1-thioglycosides: use of anomerization catalyzed by boron trifluoride

Anomeric pairs of some alkyl 1-thioaldopyranosides of d-galactose, d-glucose, d-mannose, 2-acetamido-2-deoxy-d-glucose, 2-acetamido-2-deoxy-d-galactose, and l-fucose were prepared. The per-O-acetylated, 1,2-trans anomers of 6-(trifluoroacetamido)hexyl 1-thioaldopyranosides and 5-(methoxycarbonyl)pentyl 1-thioaldopyranosides were anomerized with boron trifluoride in dichloromethane. The anomeric mixtures were then separated by chromatography, using columns of either silica gel or an ion-exchange resin. De-blocking of the separated compounds provided pure anomers of 6-aminobexyl 1-thioaldopyranosides or 5-carboxypentyl 1-thioaldopyranosides. The aglycons of the latter glycosides were further extended by reaction with aminoacetaldehyde diethyl acetal, which, after deacetalization of the products, provided an ω-aldehydo group. These series of glycosides could be readily coupled to proteins or solid matrices.     

Preparation of 1-thioglycosides having ω-aldehydo aglycons useful for attachment to proteins by reductive amination

A series of 1-thioglycosides containing an ω-aldehydo group (as the dimethyl acetal) on the aglycon were prepared by reaction of O-acetyl-1-thioaldoses with N-(chloroacetyl)aminoacetaldehyde dimethyl acetal, a compound readily prepared by the action of chloroacetyl chloride or chloroacetic anhydride on 2-aminoacetaldehyde dimethyl acetal. O-Deacetylation of the 1-thioglycosides, followed by deacetalation, yielded the desired products. An analogous 1-thioglycoside having a longer aglycon was prepared by reaction of 1-thio-D-galactose with (6-aminohexanoyl)-aminoacetaldehyde dimethyl acetal, obtained by condensing 6-bromohexanoic acid and aminoacetaldehyde with 3-(3-dimethylaminopropyl)-1-ethylcarbodiimide. These glycosides were found to be useful for modification of proteins to yield neoglyco-proteins.     

Syntheses of 1-beta-D-arabinofuranosyl-5-hydroxymethyl-N4-alkylcytosine

Starting from uridine, 1-beta-D-arabinofluranosyl-5-hydroxymethyl-N4-alkylcytosines were prepared via 1-beta-D-arabinofuranosyluracil. During the course of this synthetic work, an interesting observation has been made that 5-acetoxy group of 1-(2,3,5-tri-O-acetyl-beta-D-arabinofuranosyl)-5-acetoxymethyluracil and its derivatives was easily displaced at room temperature with alkylamine in methanol, but not in chloroform, to give the corresponding 5-alkylaminomethyl derivatives.     

Syntheses and chiroptical properties of some derivatives of 1-thioglycerol

A modified synthesis of 3-thio-sn-glycerol which leads to a product of high optical purity is described. The purity was demonstrated by the use of a chiral shift reagent. 3-S-Acetyl- and 3-S-oleyl-3-thio-sn-glycerol as well as 3-acyl derivatives of 3-thio-sn-glycerol have been synthesized. The ORD and CD curves of these compounds as well as of some other derivatives of 3-thio-sn-glycerol were analyzed and discussed. The CD curves of the triacyl derivatives show a positive effect at 260 nm and a negative effect at 230–250 nm.     

Syntheses and Biological Activities of 1-O-Glucopyranosyl Fatty Acid Esters

1-O-Palmitoyl-d-glucopyranose was prepared by the selective 1-O-acylation of 4,6-O-benzylideneglucose followed by hydrogenolysis of the protecting group. 1-O-Oleoyl-d-glucopyranose was synthesized from the corresponding benzylidene derivative by selective hydrolysis in acetic acid. This procedure constitutes a useful method for the synthesis of 1-O-acyl-d-glucopyranoses containing unsaturated carboxylic acids. However, 4,6-O-benzylidene-l-O-linolenoyl-d-glucopyranose was converted to 3-O-linolenoyl-d-glucopyranose by the acidic hydrolysis due to acyl migration.

Synthesized glucosyl esters were inactive in the bean second-internode bioassay. However, it was found that 3-O-linolenoyl-d-glucopyranose had a promoting activity on germination of pollen and growth of pollen tube.     

Efectos de la Extracción de Maderas sobre la Diversidad de Mamiferos Pequeños en Bosques de Tierras Bajas de la Guayana Venezolana1

The responses of small mammal communities to forest disturbance by logging were evaluated. The study area was located in the Imataca Forest Reserve (Venezuelan Guayana Region), where vegetation was predominantly lowland rain forest. Field analyses were based on a comparative inventory of species inhabiting primary forests and areas disturbed by selective logging. The taxonomic groups used as indicators of die ecological impact of logging belonged to the orders Didelphimorphia, Chiroptera, and Rodentia (families Sciuridae, Muridae, and Echimyidae). The following sampling methods were used: (1) mist nets; (2) traps in 2.4 ha grids (each with 120 stations: 60 at ground level and 60 in trees); and (3) diurnal and nocturnal sight surveys. Total sampling effort consisted of 1904 net‐hours, 10,320 trap‐nights, and 567 h of direct observations. At least 83 mammalian species inhabited die evaluated forests (74.7 percent corresponding to Chiroptera), of which 15.3 percent were restricted to primary forest. In logged areas, small mammal communities were characterized by: (1) higher abundances of individuals; (2) lower proportions of carnivorous and gleaning insectivorous bats; (3) increases in the relative abundance of frugivorous bat species that eat the fruits of colonizing plants; (4) higher proportions of aerial insectivores (Molossidae) at die lowest levels of die forest; (5) simplification in trophic structure of non‐volant species, widi semiarboreal predator‐omnivores being die dominant guild (followed by terrestrial frugivore‐omnivores); and (6) reduction in the relative abundance of mainly canopy‐associated species. These results are explained by: (1) lower availability of key resources associated with primary forest (e.g., roosts in hollow trunks of mature trees, canopy fruits, and tree‐crown continuity); (2) higher relative abundance of some food resources, such as terrestrial invertebrates and saprophytic plants, principally in areas where primary production is limited by low‐fertility soils; (3) increase of roosting sites under fallen trunks; (4) modification of microclimatic conditions at die understory level as a consequence of a greater incident sunlight after canopy opening; and (5) increase in density of early successional plants. The implications of these results to the conservation of biodiversity in forests managed for timber extraction in die Venezuelan Guayana Region are discussed.     

Syntheses and antifungal activity of pseudomycin side-chain analogues. Part 1

We have described herein the syntheses of three novel series of aromatic ring containing pseudomycin side-chain analogues. Preliminary biological evaluations of these analogues clearly indicate that it is possible to synthesize rigid pseudomycin side-chain analogues without compromising in vitro antifungal activity.     

Densidad Poblacional y Disponibilidad de Híbitat de la Danta de Montaña (Tapirus pinchaque) en los Andes Centrales de Colombia1

Population density of Tapirus pinchaque was estimated in 7000 ha Parque Nacional Natural Los Nevados in the central Andes of Colombia. Eight variables were measured in 110 left rear foot prints of the mountain tapir: total length and width, and length and width of the three toes. This information was analyzed with Cluster Analysis by means of UPGMA and Euclidean distance using the scores obtained by means of a Principal Component Analysis (PCA) using the eight variables. Habitat availability was measured in 147,000 ha using aerial photographs taken during the 1950s and 1980s. The results of the cluster analysis showed that there are between 11 and 15 individuals, for a mean density of one individual for each 551 ± 85 ha. The measurements of forest cover in the 147000 ha showed that habitat availability for the mountain tapir (montane forests and forestry plantations) increased 18l4lha from the 1950s to the 1980s. This increment in forest cover seems to have a positive effect on the local population size of T. pinchaque, since in areas previously covered by pastures, there are now secondary forests where tapirs tracks and feces can be found.     

Syntheses of 1,2-annulated and 1-spiroannulated carbohydrate derivatives: recent developments

A variety of different strategies has been used for the 1,2-annulation and the 1-spiroannulation of further rings to monosaccharides. This short review presents some recent methods to access such structures involving radical chemistry, cycloadditions, Michael reactions and metal-catalyzed transformations.     

Syntheses of sulfated glycopolymers and analyses of their BACE-1 inhibitory activity

The glycopolymers for glycosaminoglycan mimic were synthesized, and the inhibitory effects of Alzheimer’s β-secretase (BACE-1) were examined. The regio-selective sulfation was conducted on N-acetyl glucosamine (GlcNAc), and the acrylamide derivatives were synthesized with the consequent sulfated GlcNAc. The glycopolymers were synthesized with acrylamide using radical initiator. The glycopolymer with sulfated GlcNAc showed the strong inhibitory effect on BACE-1, and the inhibitory effects were dependent on the sulfation positions. Especially, glycopolymers carrying 3,4,6-O-sulfo-GlcNAc showed the strong inhibitory effect. The docking simulation suggested that glycopolymers bind to the active site of BACE-1.