86747-82-2

Upstream product

• 4148-58-7 (4aR,6S,7S,8R,8aS)-6-Methoxy-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxine-7,8-diol 
• 16475-29-9 phenylchlorosulfate 
• 4288-93-1 methyl 4,6-O-benzylidene-α-D-galactopyranoside 
• 3162-96-7 methyl 4,6-O-benzylidene-β-D-galactopyranoside 
• 86747-78-6 Methyl 4,6-O-Benzylidene-α-D-manno-pyranoside 2,3-Cyclic Sulfite 

Downstream Products

• 23346-01-2 4,6-O-Benzylidene-1,2-dideoxy-D-erythro-hex-1-enopyranos-3-ulose 

Relevant academic research and scientific papers

REACTIONS OF PHENYL CHLOROSULFATE AT OH-2 AND OH-3 OF ALDOHEXOPYRANOSE DERIVATIVES. COMPETING SUBSTITUTION AND DISPLACEMENT REACTIONS

Reactions of phenyl chlorosulfate-sodium hydride with methyl 4,6-O-benzylidenealdohexopyranosides are characterized by a variety of nucleophilic substitution and displacement processes involving OH-2 and -3 of the glycosides.Depending on such factors as the relative rates of substitution of these two hydroxyl groups and their configurations, as well as temperature and stoichiometry, the products may be mono- or di-phenylsulfates (or both), 2,3-cyclic sulfates, or 2,3-oxiranes.For example, in the reaction of methyl 4,6-O-benzylidene-α-D-glucopyranoside with two equivalents of phenyl chlorosulfate at +25deg, the products were the 2,3-disulfate (10percent), 2,3-cyclic sulfate (77percent), and 2,3-allo epoxide (4percent), whereas, at -25deg, by far the major product was the 2-phenylsulfate (79percent).Intramolecular displacement was so readily facilitated in the reaction of methyl 4,6-O-benzylidene-α-D-altropyranoside that the only products obtained were the 2,3-anhydro-manno- (major) and -allo-pyranosides.Conformations of the 2,3-cyclic sulfates are considered on the basis of their n.m.r. characteristics.

Cyclic Sulfur Esters as Substrates for Nucleophilic Substitution. A New Synthesis of 2-Deoxy-2-fluoro-D-glucose

The 2,3-cyclic sulfites and sulfates of methyl 4,6-O-benzylidene-α- and -β-D-mannopyranoside were synthesized and examined as suitable substrates for the preparation of 2-deoxy-2-fluoro-D-glucose.Both sulfites on reaction with tetramethylammonium fluoride gave reaction products due to attack at sulfur by water.The methyl α-D-glycoside sulfate gave an α,β-unsaturated ketone (7).The β-methyl sulfate reacted cleanly with fluoride and other nucleophiles to give, after hydrolysis, the 2-substituted 2-deoxyglucose compounds.