The total synthesis of mixed‐sequence alginate oligosaccharides, featuring both β‐D ‐mannuronic acid (M) and α‐L ‐guluronic acid (G), is reported for the first time. A set of GM, GMG, GMGM, GMGMG, GMGMGM, GMGMGMG, and GMGGMG alginates was assembled using GM building blocks, having a guluronic acid acceptor part and a mannuronic acid donor side to allow the fully stereoselective construction of the cis‐glycosidic linkages. It was found that the nature of the reducing‐end anomeric center, which is ten atoms away from the reacting alcohol group in the key disaccharide acceptor, had a tremendous effect on the efficiency with which the building blocks were united. This chiral center determines the overall shape of the acceptor and it is revealed that the conformational flexibility of the acceptor is an all‐important factor in determining the outcome of a glycosylation reaction. 相似文献
A de novo synthetic method towards apiose, a structurally unusual furanose, is reported. The key feature is sequential metal catalysis consisting of the palladium‐catalyzed asymmetric intermolecular hydroalkoxylation of an alkoxyallene and subsequent ring‐closing metathesis (RCM). This strategy enabled the efficient synthesis of various apiose‐containing disaccharides and a unique convergent synthesis of trisaccharides. 相似文献
The importance of carbohydrates is evident by their essential role in all living systems. Their syntheses have attracted attention from chemists for over a century. Most chemical syntheses in this area focus on the preparation of carbohydrates from naturally occurring monosaccharides. De novo chemical synthesis of carbohydrates from feedstock starting materials has emerged as a complementary method for the preparation of diverse mono‐ and oligosaccharides. In this review, the history of de novo carbohydrate synthesis is briefly discussed and particular attention is given to methods that address the formation of glycosidic bonds for potential de novo synthesis of oligosaccharides. Almost all methods of this kind involve the formation of dihydropyran intermediates. Recent progress in forming dihydropyrans by Achmatowicz rearrangement, hetero‐Diels–Alder cycloaddition, ring‐closing metathesis, and other methods is also elaborated. 相似文献
The scarcity and expense of access to L ‐sugars and other rare sugars have prevented the exploitation of their biological potential; for example D ‐psicose, only recently available, has been recognized as an important new food. Here we give the definitive and cheap synthesis of 99.4% pure L ‐glucose from D ‐glucose which requires purification of neither intermediates nor final product other than extraction into and removal of solvents; a simple crystallization will raise the purity to >99.8%. 相似文献
A sol‐gel technique was used here to prepare a renewable carbon ceramic electrode modified with nickel powder. Cyclic voltammograms of the resulting modified electrode show stable and a well defined redox couple due to Ni(II)/Ni(III) system with surface confined characteristics. The modified electrode shows excellent catalytic activity toward L ‐cystine, L ‐cysteine and L ‐methionine oxidation at reduced overpotential in alkaline solutions. In addition the antifouling properties at the modified electrode toward the above analytes and their oxidation products increases the reproducibility of results. L ‐cystine, L ‐cysteine and L ‐methionine were determined chronoamperometricaly at the surface of this modified electrode at pH range 9–13. Under the optimized conditions the calibration curves are linear in the concentration range 1–450 μM, 2–90 μM and 0.2–75 μM for L ‐cystine, L ‐methionine and L ‐cysteine determination, respectively. The detection limit and sensitivity were 0.64 μM, 3.8 nA/ μM for L ‐cystine, 2 μM, 5.6 nA/ μM for L ‐methionine and 0.2 μM and 8.1 nA/μM for L ‐cysteine. The advantageous of this modified electrode is high response, good stability and reproducibility, excellent catalytic activity for oxidation inert molecules at reduced overpotential and possibility of regeneration of the electrode surface by potential cycling for 5 minutes. Furthermore, the modified electrode has been prepared without using specific reagents. This sensor can be used as an amperometric detector for disulfides detection in chromatographic or flow systems. 相似文献
Crystals of maleates of three amino acids with hydrophobic side chains [L‐leucenium hydrogen maleate, C6H14NO2+·C4H3O4−, (I), L‐isoleucenium hydrogen maleate hemihydrate, C6H14NO2+·C4H3O4−·0.5H2O, (II), and L‐norvalinium hydrogen maleate–L‐norvaline (1/1), C5H11NO2+·C4H3O4−·C5H12NO2, (III)], were obtained. The new structures contain C22(12) chains, or variants thereof, that are a common feature in the crystal structures of amino acid maleates. The L‐leucenium salt is remarkable due to a large number of symmetrically non‐equivalent units (Z′ = 3). The L‐isoleucenium salt is a hydrate despite the fact that L‐isoleucine is a nonpolar hydrophobic amino acid (previously known amino acid maleates formed hydrates only with lysine and histidine, which are polar and hydrophilic). The L‐norvalinium salt provides the first example where the dimeric cation L‐Nva...L‐NvaH+ was observed. All three compounds have layered noncentrosymmetric structures. Preliminary tests have shown the presence of the second harmonic generation (SGH) effect for all three compounds. 相似文献
An efficient synthesis of 1,2,3,4,6‐penta‐O‐acetyl‐L ‐idopyranose 2 from 3,5‐O‐benzylidene‐1,2‐O‐isopropylidene‐α‐D ‐glucofuranose in five steps in 45% overall yield via hydroboration of enol ether, hydrolysis of L ‐idofuranosyl sugar and acetolysis of 1,6‐anhydro‐β‐L ‐idopyranose as key steps is described here. 相似文献
Three types of copolymers of poly(L ‐lactic acid) (PLLA) were synthesized by direct polycondensation of L ‐lactic acid and phenyl‐substituted α‐hydroxy acids (L ‐phenyllactic acid and D ‐ and L ‐mandelic acids). It was found that the glass transition temperature of the copolymers comprising L ‐mandelic acid became significantly higher (from 58 to 69 °C) with increasing content of L ‐mandelic acid (from 0 to 50 mol‐%) although the Mw decreased (from 87 000 to 4 000 Da). The cast films of the L ‐mandelic acid containing copolymers showed improved tensile properties compared with those of the PLLA film. This may be due to a pinning effect of the L ‐mandelic acid units on the helix formation of PLLA, although 30% of the units were racemized. The enzymatic degradability of the L ‐mandelic acid containing copolymers was much higher than that of PLLA, as analyzed with Proteinase K® originating from Tritirachium album.
Synthesis of copolymers of L ‐lactic acid and phenyl‐substituted α‐hydroxy acids. 相似文献
Practical syntheses of 2‐keto‐3‐deoxy‐D ‐xylonate (D ‐KDX) and 2‐keto‐3‐deoxy‐L ‐arabinonate (L ‐KDA) that rely on reaction of the anion of ethyl 2‐[(tert‐butyldimethylsilyl)oxy]‐2‐(dimethoxy phosphoryl) acetate with enantiopure glyceraldehyde acetonide, followed by global deprotection of the resultant O‐silyl‐enol esters, have been developed. This has enabled us to confirm that a 2‐keto‐3‐deoxy‐D ‐gluconate aldolase from the archaeon Sulfolobus solfataricus demonstrates good activity for catalysis of the retro‐aldol cleavage of both these enantiomers to afford pyruvate and glycolaldehyde. The stereochemical promiscuity of this aldolase towards these enantiomeric aldol substrates confirms that this organism employs a metabolically promiscuous pathway to catabolise the C5‐sugars D ‐xylose and L ‐arabinose. 相似文献
A fast chemoenzymatic synthesis of sialylated oligosaccharides containing C5‐modified neuraminic acids is reported. Analogues of GM3 and GM2 ganglioside saccharidic portions where the acetyl group of NeuNAc has been replaced by a phenylacetyl (PhAc) or a propanoyl (Prop) moiety have been efficiently prepared with metabolically engineered E. coli bacteria. GM3 analogues were either obtained by chemoselective modification of biosynthetic N‐acetyl‐sialyllactoside (GM3NAc) or by direct bacterial synthesis using C5‐modified neuraminic acid precursors. The latter strategy proved to be very versatile as it led to an efficient synthesis of GM2 analogues. These glycomimetics were assessed against hemagglutinins and sialidases. In particular, the GM3NPhAc displayed a binding affinity for Maackia amurensis agglutinin (MAA) similar to that of GM3NAc, while being resistant to hydrolysis by Vibrio cholerae (VC) neuraminidase. A preliminary study with influenza viruses also confirmed a selective inhibition of N1 neuraminidase by GM3NPhAc, suggesting potential developments for the detection of flu viruses and for fighting them. 相似文献
A modified electrode was fabricated by grafting of poly (2,6‐pyridinedicarboxylic acid) film (PDC) by electropolymerization of 2,6‐pyridinedicarboxylic acid on the glassy carbon electrode (GCE). Then, gold nanoparticles (NG) and 1,2‐naphthoquinone‐4‐sulfonic acid sodium (Nq) were immobilized on the PDC/GCE to prepare Nq/NG/PDC/GCE by immersing electrode into NG and Nq solution, respectively. The Nq species on NG/PDC/GCE could catalyze electrooxidation of N‐acetyl‐L ‐cysteine (NAC) with lowering the over potential by about 600 mV. This method used for detection of NAC in dynamic range from 4.0×10?6 M to 1.30×10?4 M with a detection of limit (2σ) 8.0×10?7 M. 相似文献
D‐Deoxyribose, the basic structure unit of DNA, and its antipode L‐deoxyribose were concisely synthesized from easily available D‐ and L‐glyceralaldehydes using a known convenient diastereoselective propargylation as the key step. 相似文献