Efficient chemical synthesis of both anomers of ADP l-glycero- and d-glycero-d-manno-heptopyranose

Stereospecific synthesis of sugar-1-phosphates and their conversion to sugar nucleotides

“…doi:10.1016/j.carres.2008.01.046 used to prepare sugar nucleotides, initially developed by Moffatt and Khorana, 23 involves the coupling of sugar-1-phosphates with electrophilic nucleoside 5 0 -monophosphates, frequently activated as morpholidate or imidazolide esters. 24 Although improved yields have been reported using 1H-tetrazole as a catalyst 25 or through extensive co-evaporations with pyridine, 26 many coupling reactions of this type take several days to reach completion and result in only low to moderate yields (<50%) following purification. [27][28][29][30][31] Herein, we report the synthesis and purification of eight sugar nucleotides via coupling of sugar-1-phosphates with nucleoside 5 0 -monophosphates activated using trifluoroacetic anhydride and N-methylimidazole.…”

Stereocontrolled Synthesis of the d- and l-glycero-β-d-manno-Heptopyranosides and Their 6-Deoxy Analogues. Synthesis of Methyl α-l-Rhamno-pyranosyl-(1→3)-d-glycero-β-d-manno-heptopyranosyl- (1→3)-6-deoxy-glycero-β-d-manno-heptopyranosyl-(1→4)-α-l- rhamno-pyranoside, a Tetrasaccharide Subunit of the Lipopolysaccharide from Plesimonas shigelloides

“…2 The synthesis of higher carbon sugars such as heptoses has been investigated for more than a century, 4 and several methods have been developed. 2,4,5 The synthesis of a large number of complex oligosaccharides containing α-L,D-or α-D,Dheptopyranosides (Hepp), has been achieved by 6 Plesimonas shigelloides is a Gram-negative, flagellated, rod-shaped bacterium which has been isolated from a variety of sources such as freshwater, surface water, and many wild and domestic animals. The infections correlate strongly with the surface water contamination, and are particularly common in tropical and subtropical habitats.…”

Polyphosphates and Pyrophosphates of Hexopyranoses as Allosteric Effectors of Human Hemoglobin: Synthesis, Molecular Recognition, and Effect on Oxygen Release

“…[33d, 35,36] These characteristic features also apply for our derivatives, both protected phosphorylated (19,20,25,26) and sodium salts (31,32), as shown in Table 1.…”

“…The anomeric configuration of the phosphates was, however, unambiguously established on the basis of the values of the heteronuclear coupling constant J C-1,H-1 , which was 174 and 175 Hz for compounds 31 and 49 respectively, indicating an a-phosphate, and 160 Hz for compound 32, indicating a b-anomer. [35] To gain access to 2,3,4,6-tetrakis phosphorylated glucose and mannose derivatives, the commercially available glycosides 35 and 36 were used (Scheme 3). The free hydroxy groups in 35 and 36 were all simultaneously phosphorylated (compounds 37 and 38) under the standard protocol (in 94 and 79 % yields, respectively) to give, via the triethylammonium salts 39 and 40, the final sodium salts 41 and 42 in excellent overall yields.…”