2,5-Anhydro-2-C-(hydroxymethyl)-3,4,6-tris-O-(phenylmethyl)-D-arabino-hexitol → 2,5-anhydro-2-C-(hydroxymethyl)-D-glucitol

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Reaction Steps

In accordance with Flowchart G, 2,5-anhydro-2-C-(hydroxymethyl)-3,4,6-tris-O-(phenylmethyl)-D-glucitol 42 is hydrogenated in methanol/acetic acid over palladium on carbon, giving 2,5-anhydro-2-C-(hydroxymethyl)-D-glucitol 51, which is treated with copper sulfate and sulfuric acid in acetone, then neutralized, giving 2,5-anhydro-2-C-(hydroxymethyl)-21,3-O-(1-methylethylidene)-D-glucitol 52. Compound 52 is reacted with diphenyl phosphorochloridate in pyridine at reduced temperature, giving 2,5-anhydro-2-C-[[(diphenoxyphosphinyl)oxy]methyl]-1,3-O-(1-methylethylidene)-D-glucitol, 6-(diphenyl phosphate) 53, which is then treated with 80% aqueous acetic acid at 80° C., giving 2,5-anhydro-2-C-[[(diphenoxyphosphinyl)oxy]methyl]-D-glucitol, 6-(diphenyl phosphate) 54. Substitution of other esterifying agents as described in Flowchart A will result in the corresponding tetraesters. Compound 53 is hydrogenated in methanol over platinum oxide, giving directly the product 2,5-anhydro-2-C-[(phosphonooxy)methyl]-D-glucitol, 6-(dihydrogen phosphate) 55. Compound 54 may be hydrogenated under the same conditions, giving 55. ##STR20##

Provenance & Evidence