2,5-anhydro-3,4,6-tris-O-(phenylmethyl)-D-mannose → 2,5-anhydro-1,3,4-tris-O-(phenylmethyl)-D-mannitol

HRID 1073447Notes

Reaction equation

HRID 1073447 reaction equation
[C:1]1([CH2:7][O:8][C@H:9]2[C@H:15]([O:16][CH2:17][C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[C@@H:14]([CH2:24][O:25][CH2:26][C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)[O:13][C@@H:10]2[CH:11]=[O:12])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-]>CCOCC>[C:27]1([CH2:26][O:25][CH2:24][C@H:14]2[O:13][C@H:10]([CH2:11][OH:12])[C@@H:9]([O:8][CH2:7][C:1]3[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=3)[C@@H:15]2[O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1

Participants

4

Reactant 2

HCID 108364862,5-anhydro-3,4,6-tris-O-(phenylmethyl)-D-mannoseHCID 21226445Aluminium lithium hydride

Product 1

HCID 103207312,5-anhydro-1,3,4-tris-O-(phenylmethyl)-D-mannitol

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

In accordance with Flowchart E, 2,5-anhydro-3,4,6-tris-O-(phenylmethyl)-D-mannose 29 is reacted with lithium aluminum hydride in ether at reflux temperature under argon, giving 2,5-anhydro-1,3,4-tris-O-(phenylmethyl)-D-mannitol 38. Compound 38 is hydrogenated in methanol/acetic acid over palladium on carbon, giving 2,5-anhydro-D-mannitol 39, which is then reacted with diphenyl phosphorochloridate in pyridine at reduced temperature, giving the product of Formula I where R', R",R'" and R"" are phenyl, 2,5-anhydro-D-mannitol, 1,6-bis(diphenyl phosphate) 40. Compound 40 is hydrogenated in methanol over platinum oxide, giving the product of Formula I where R', R",R'" and R"" are hydrogen, 2,5-anhydro-D-mannitol, 1,6-bis(dihydrogen phosphate) 41. Compounds 40 and 41 are disclosed in Voll et al., Carbohydrate Research, 95, 145-154 (1981), but are prepared by a different process. Substituting other phosphorylating agents in the reaction from 39 to 40, as described in Flowchart A, will result in the corresponding tetraesters and mixed tetraesters. ##STR18##

Workup

  1. temperatureat reflux temperature under argon

Sources & evidence

ORD record
ord-ae1fd56f37064d6b8cfeb0bbca13dc98
Source dataset
uspto-grants-1990_11
Patent number
US04968790

Reaction notes

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