2,5-Anhydro-2-C-(hydroxymethyl)-3,4,6-tris-O-(phenylmethyl)-D-arabino-hexitol → 2,5-anhydro-2-C-(hydroxymethyl)-D-glucitol
Reaction equation
[OH:1][CH2:2][C:3]1([O:25][C@H:24]([CH2:26][O:27]CC2C=CC=CC=2)[C@@H:15]([O:16]CC2C=CC=CC=2)[C@@H:6]1[O:7]CC1C=CC=CC=1)[CH2:4][OH:5]>CO.C(O)(=O)C.[Pd]>[OH:1][CH2:2][C:3]1([O:25][C@H:24]([CH2:26][OH:27])[C@@H:15]([OH:16])[C@@H:6]1[OH:7])[CH2:4][OH:5]Participants
Procedure
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##
Sources & evidence
- ORD record
- ord-844174e582a542359c25e81d1f3352a3
- Source dataset
- uspto-grants-1990_11
- Patent number
- US04968790
Reaction notes
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