Imidazole carbohydrate

TIPDSCI2, DMF, imidazole. This reagent is primarily used in carbohydrate protection, but occasionally it proves valuable in other circumstance s." ... 

Because sugars are involved in most of the mechanisms established for the synthesis of these heterocycles, the development of carbohydrate chemistry has been most helpful in these researches—especially for the preparation of specifically labeled molecules. Conversely, the contribution of these efforts to carbohydrate chemistry and biochemistry has shown the involvement in biosynthesis of 1 -deoxy-D-f/rreo-pentulose—scarcely before recognized and considered a rare sugar—and of fully functionalized pentuloses of still unknown configuration (or their phosphates). Finally, evidence has been found in prokaryotes for a most extraordinary transformation of 5-amino-l-(P-D-ribofuranosyl)imidazole 5 -phos-phate into a pyrimidine. Surely, this transformation should be explained in terms... 

Biosorption is a rather complex process affected by several factors that include different binding mechanisms (Figure 10.4). Most of the functional groups responsible for metal binding are found in cell walls and include carboxyl, hydroxyl, sulfate, sulfhydryl, phosphate, amino, amide, imine, and imidazol moieties.4 90 The cell wall of plant biomass has proteins, lipids, carbohydrate polymers (cellulose, xylane, mannan, etc.), and inorganic ions of Ca(II), Mg(II), and so on. The carboxylic and phosphate groups in the cell wall are the main acidic functional groups that affect directly the adsorption capacity of the biomass.101... 

The Tsuji-Trost reaction is the Pd(0)-catalyzed allylation of a nucleophile [48-51]. The NH group in imidazole can take part as a nucleophile in the Tsuji-Trost reaction, whose applications are found in both nucleoside and carbohydrate chemistry. Starting from cyclopentadiene and paraformaldehyde, cyclopentenyl allylic acetate 64 was prepared in diastereomerically-enriched form via a Prins reaction [52], Treating 64 with imidazole under Pd(0) catalysis provided the N-alkylated imidazole 65. 

In the carbohydrate chemistry arena, the Tsuji-Trost reaction has been applied to construct N-glycosidic bonds [53]. In the presence of Pd2(dba>3, the reaction of 2,3-unsaturated hexopyranoside 68 and imidazole afforded N-glycopyranoside 69 regiospecifically at the anomeric center with retention of configuration. In terms of the stereochemistry, the oxidative addition of allylic substrate 68 to Pd(0) formed the jc-allyl complex with inversion of configuration, then nucleophilic attack by imidazole proceeded with another inversion of the configuration. Therefore, the overall stereochemical outcome is retention of configuration. 

A number of other substituted imidazolium ions have also been reported. [MIM-C2H50CH3]Br and [MIM-CH30CH3]Br, liquids at room temperature, were recently reported to be good solvents for carbohydrates and proteins (47). The diversity of organic cations was extended even to include the antifungal drug miconazole, which contains an imidazole ring. By the reaction of the miconazole with alkyl iodide, bioactive cations were obtained that were subsequently used to form ionic liquids with PF (9). 

Complexes of maltose with urea, thiourea, imidazole, methanol, 2-oxazolidinone, N,N-dimethylformamide, and hexamethylphosphoric triamide have been described.131 These complexes were noncrystalline and hygroscopic. Such complex-forming reactions could be valuable in the preservation of food flavors during the dehydration process. Sugars have been shown to complex with ethylenediamine.133,133 The nature of the complex has been suggested to be that of a proton-transfer type, in which the carbohydrate moiety is the proton donor and the amine is the proton acceptor. 

Two methods have been developed for preparing carbohydrate imidazole-l-sulfonates [68] (Scheme 6). The first, (method A) consists in allowing a partially protected sugar to react with 1.5 eq. of sulfuryl chloride in dimethylformamide (DMF) at —40°C in the presence... 

Many groups in proteins, carbohydrates, and nucleic acids form hydrogen bonds to one another and to surrounding water molecules. For example, an imidazole group of a protein can bond to an OH group of an amino acid side chain or of water in the following ways ... 

The imidazole part of the IQ-compounds suggests creatinine as a common precursor. The remaining parts of the IQ-compounds could arise from Maillard reaction products, e.g., 2-methylpyri-dine or 2,5-dimethylpyrazine. These two compounds could be formed through Strecker degradation. In Maillard reactions, this is induced by a-dicarbonyl compounds derived from carbohydrates, which are thereby converted to pyrroles, pyridines, pyrazines, etc. (8). 

Hereafter the anomeric center is protected. When the ceramide building block has to be connected to the oligosaccharide, normally selectively deprotection of the C-la position of the lactose is necessary. The thexyldimethylsilyl (TDS) group is a less common trialkylsilyl protecting group in carbohydrate synthesis. Advantageously it survives some rather harsh conditions. The liquid TDSC1 42 with imidazole 43 or DMAP as basic activator in a dipolar aprotic solvent like DMF forms the C-l protected compound 8 as a mixture of anomers.21... 

An enantiospecific synthesis of negstatin I (52) was accomplished efficiently with a sequence involving two C-imidazolide anion transformations. The first was coupling of a suitably protected carbohydrate intermediate with N-tritylimidazole. Direct monobromination of imidazole (51a, X = Y = H) was not feasible, except by selective halogen-metal exchange and reprotonation of dibromo intermediate (51b, X = Y = Br) [95TL6721], Introduction of the pendant acetic acid function was accomplished by C-allylation of 51c. 

Silyl ethers, such as TMS, triethylsilyl (TES), triisopropylsilyl (TIPS), lerl-butyldi-methylsilyl (TBS), and terl-butyldiphenylsilyl (TBDPS) ethers (Scheme 2.6), are frequently used in carbohydrate chemistry due to their unique reactivity and steric effect (see Section 2.4.1) [1, 2], These groups are typically introduced onto the molecule by treatment with the corresponding silyl halide or triflate (OTf) and a base, such as Et3N, pyridine, 2,6-lutidine, or imidazole. 

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