Two methyl anhydro-d-fructopyranosides prepared from d-mannitol

✍ Scribed by Henry B. Sinclair

• Book ID: 102993613
• Publisher: Elsevier Science
• Year: 1988
• Tongue: English
• Weight: 653 KB
• Volume: 181
• Category: Article
• ISSN: 0008-6215
• DOI: 10.1016/0008-6215(88)84027-8

✦ Synopsis

D-Mannitol

(1) was converted into 1,5-anhydro-r~-mannitol, which was treated consecutively with p-toluenesulfonyl chloride (1 mol. equiv.) and benzoyl chloride (3 mol. equiv.), to produce 1,5-anhydro-2,3,4-tri-0-benzoyl-6-O-p-tolylsulfonyl-D-mannitol.

1,5-Anhydro-2,3,4-tri-O-benzoyl-6-deoxy-6-iodo-D-mannitol (4) was prepared by displacing the p-tolylsulfonyl group by reaction with sodium iodide. 1,5-Diazabicyclo[5.4.0]undec-5-ene eliminated hydrogen iodide from 4, to yield 1,5-anhydro-2,3,4-tri-O-benzoyl-6-deoxy-~-lyno-hex-5-enitol (5). Addition of bromine to a methanolic solution in 5 in the presence of potassium carbonate resulted in a separable mixture of methyl 1-bromo-l-deoxy-a-D-fructopyranoside (6) and methyl 1-bromo-1-deoxy+-D-fructopyranoside (8). Dilute alkali converted 6 into methyl 1,3-anhydro-cu-D-fructopyranoside, identified as its 4,5-diacetate. Dilute alkali converted 8 into methyl 1,4-anhydro-P-D-fructopyranoside.

Coupling constants (Hz)