128473-04-1

Upstream product

• 838-85-7 diphenyl hydrogen phosphate 
• 128571-86-8 2,3,4-tri-O-acetyl-α-L-fucopyranosyl trichloroacetimidate 
• 64913-16-2 L-fucose tetraacetate 
• 7404-35-5 1,2,3,4-tetra-O-acetyl-L-fucopyranose 
• 226570-52-1 tri-O-acetyl-α-L-fucopyranosyl nitrate 
• 28915-80-2 2,3,4-tri-O-acetyl-L-fucopyranose 
• 2524-64-3 chlorophosphoric acid diphenyl ester 
• 16741-27-8 2,3,4-tri-O-acetyl-α-L-fucopyranosyl bromide 

Downstream Products

• 95581-07-0 2,3,4-tri-O-acetyl-1-azido-1-deoxy-β-L-fucopyranose 

Relevant academic research and scientific papers

The use of cesium dibenzyl and diphenyl phosphates for stereoselective synthesis of glycosyl phosphate derivatives

Peracetates of β-glycosyl dibenzyl phosphates are formed efficiently in the reaction of cesium dibenzyl phosphate with peracetyl-α-glycosyl nitrates derived from L-fucopyranose, D-galactopyranose, and 2-azido-2-deoxy-D-galactopyranose or with tri-O-acetyl-α-L-fucopyranosyl bromide. On the contrary, the reaction of the above-mentioned glycosyl nitrates with cesium diphenyl phosphate leads to thermodynamically more stable α-glycosyl diphenyl phosphate via intermediate formation of the corresponding β-anomers.

Synthesis of glycosyl phosphates from acetylated glycosyl nitrates

Acetylated α-glycosyl nitrates were efficiently converted under mild conditions into protected β-glycosyl phosphates by treatment with cesium dibenzyl phosphate or into thermodynamically more stable α-glycosyl phosphate derivatives upon interaction with cesium diphenyl phosphate. These reactions were found to be applicable both to 2-azido-2,6-dideoxy- and 2-azido-2-deoxygalactopyranosyl nitrates as well as to 6-deoxygalactopyranosyl and galactopyranosyl derivatives.

Process for the stereoselective preparation of β-fucopyranosyl phosphates and very pure GDP-fucose

The invention relates to a process for the stereoselective preparation of β-L-fucopyranosyl phosphates via the trichloroacetimidates of protected L-fucose and the synthesis and purification of very pure GDP-fucose from the β-L-fucopyranosyl phosphates.

Synthesis of glycosyl phosphates and azides

Anomerically enriched diphenyl hexopyranosyl phosphate triesters have been prepared from O-alkyl and -acylated hexopyranoses, using diphenyl chlorophosphate and 4-N,N-dimethylaminopyridine. Glycosyl phosphate triesters of D-gluco-, D-galacto-, D-manno, 2-acetamido-2-deoxy-D-gluco-, L-fuco-, and L-rhamno-pyranosyl derivatives have been obtained by this procedure. At temperatures 0° and above, and under thermodynamic control, diphenyl glycosyl phosphates cis to the pyranosyl C-2 substituent are formed predominantly, whereas at low temperatures and under kinetic control, glycosyl phosphate triesters having 2-trans stereochemistry are obtained. The β-glycosyl phosphate triesters of D-glucose and D-galactose derivatives are unstable and undergo anomerization to the α-glycosyl phosphate triesters, in contrast to the stable β-phosphate derivatives of L-rhamnose and D-mannose. These phosphate triesters have been deprotected to glycosyl phosphate triethylammonium salts, suitable for the preparation of other key biological derivatives, such as nucleotide sugars. In addition, the diphenyl phosphate groups at the anomeric center have been displaced by azide togive the glycosyl azides, key intermediates in the synthesis of glycosyl amino acids. Anomerically enriched diphenyl hexopyranosyl phosphate triesters have been prepared from O-alkyl and -acrylated hexopyranoses, using diphenyl chlorophosphate and 4-N,N-dimethylaminopyridine. Glycosyl phosphate triesters of D-gluco-, D-galacto-, D-manno, 2-acetamido-2-deoxy-D-gluco-, L-fuco-, and L-rhamno-pyranosyl derivatives have been obtained by this procedure. At temperatures 0° and above, and under thermodynamic control, diphenyl glycosyl phosphates cis to the pyranosyl C-2 substituent are formed predominantly, whereas at low temperatures and under kinetic control, glycosyl phosphate triesters having 1,2-trans stereochemistry are obtained. The β-glycosyl phosphate triesters of D-glucose and D-galactose derivatives are unstable and undergo anomerization to the α-glycosyl phosphate triesters, in contrast to the stable β-phosphate derivatives of L-rhamnose and D-mannose. These phosphate triesters have been deprotected to glycosyl phosphate triethylammonium salts, suitable for the preparation of other key biological derivatives, such as nucleotide sugars. In addition, the diphenyl phosphate groups at the anomeric center have been displaced by azide to give the glycosyl azides, key intermediates in the synthesis of glycosyl amino acids.

Glycosyl Imidates, 47. Stereospecific Synthesis of α- and β-L-Fucopyranosyl Phosphates and of GDP-Fucose via Trichloroacetimidate

Reaction of the benzyl- and acetyl-protected α-trichloroacetimidates 1 and 6α with dialkyl and diaryl phosphates in the presence of traces of acid affords stereoselectively the thermodynamically more stable α-L-fucopyranosyl phosphates 2, 7 and 8, respect