287733-97-5

Upstream product

• 4132-28-9 2,3,4,6-tetra-O-benzyl-D-mannopyranose 
• 92619-92-6 3,4,5,7-tetra-O-benzyl-1,2-dideoxy-D-manno-hept-1-enitol 

Downstream Products

• 300807-68-5 Phosphoric acid (2R,3R,4R,5R)-3,4-bis-benzyloxy-5-benzyloxymethyl-tetrahydro-furan-2-ylmethyl ester diphenyl ester 
• 102208-55-9 2,5-anhydro-3,4,6-tri-O-benzyl-D-mannitol 
• 94273-27-5 2,5-anhydro-3,4,6-tris-O-(phenylmethyl)-D-mannose 
• 129173-16-6 3,6-anhydro-4,5,7-tri-O-benzyl-1,2-dideoxy-D-manno-hept-1-enitol 

Relevant academic research and scientific papers

Synthesis of 2-O-(3-O-carbamoyl-α-D-mannopyranosyl)-L-gulopyranose: Sugar moiety of antitumor antibiotic bleomycin

A new route to the disaccharide moiety (2-O-(3-O-carbamoyl-α-D-mannopyranosyl)-L-gulopyranose) of the antitumor agent bleomycin was developed. Both the L-gulose synthon 21 and the 3-O-carbamoyl-D-mannose segment 30 were prepared from D-mannose in a regioselective manner by applying stannylene acetal methodology. Glycosylation of 21 with 30 proceeded smoothly, and further conversion to disaccharide derivatives (33 and 34) was successfully accomplished.

Synthesis of Selectively Labeled D-Fructose and D-Fructose Phosphate Analogues Locked in the Cyclic Furanose Form

2,5-Anhydroglucitol and 2,5-anhydromannitol and their 6-phosphate and 1,6-diphosphate derivatives are cyclic analogues of the α and β anomers of D-fructofuranose, D-fructofuranose-6-phosphate, and D-fructofuranose-1,6-diphosphate. They were synthesized from protected D-mannose or D-glucose. The synthetic method was developed with emphasis on selective 2H labeling of these compounds, as a model for 3H incorporation, which will be used for further biochemical studies. A key cyclization step, based on a benzyl ether nucleophilic attack on an activated alcohol, constructed the ring system. The stereochemistry at C2 (α/β anomers) and at C5 (D sugar) was controlled by selective epimerizations. Mono- and diphosphate analogues were obtained from the same intermediate by changing the sequence of deprotection and phosphorylation steps.

An unexpected rearrangement during Mitsunobu epimerization reaction of sugar derivatives

Mitsunobu reaction on the glucose derivative (3S,4R,5R,6R)-3,4,5,7- tetrabenzyloxy-6-hydroxy-1-heptene yielded an unexpected rearrangement major product. Its structure was determined as (3R,4R,5R,6S)-4,5,6,7- tetrabenzyloxy-3-hydroxy-1-heptene. The suggested rearrangement mechanism involves an initial intramolecular cyclization, followed by ring opening by the nucleophile p-nitrobenzoate. Product distribution of the Mitsunobu reaction was substrate-dependent, with the corresponding mannose derivative (the 3R epimer) giving less of the initial intramolecular reaction products and the corresponding galactose derivative (the 5S epimer) yielding almost exclusively the expected epimerization product. Varying the Mitsunobu reaction conditions (addition of base and using nonpolar solvent) led to the expected epimerization product of the glucose derivative.