D-Mannopyranosyl bromide, tetraacetate → HCID 69736117, compound

Reaction equation

[C:1]([O:4][C@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=O)[CH3:22])[O:7][CH:6]1Br)(=[O:3])[CH3:2].C([CH:28]1[CH:33](O)[CH:32](O)[CH:31](O)[CH:30]([CH2:37]O)O1)C=C>>[C:30]1([CH:6]2[O:7][CH:8]([CH2:19][OH:20])[CH:9]([OH:15])[CH:10]([OH:11])[CH:5]2[OH:4])[CH:31]=[CH:32][CH:33]=[CH:28][CH:37]=1.[C:12]([O:11][CH:10]1[CH:5]([O:4][C:1](=[O:3])[CH3:2])[CH:6]([C:31]2[CH:30]=[CH:37][CH:28]=[CH:33][CH:32]=2)[O:7][CH:8]([CH2:19][O:20][C:21]([C:22]2[CH:5]=[CH:10][CH:9]=[CH:8][CH:19]=2)([C:30]2[CH:31]=[CH:32][CH:33]=[CH:28][CH:37]=2)[C:31]2[CH:30]=[CH:37][CH:28]=[CH:33][CH:32]=2)[CH:9]1[O:15][C:16](=[O:18])[CH3:17])(=[O:14])[CH3:13]

Participants

Reactant 2

HCID 11441268D-Mannopyranosyl bromide, tetraacetate

HCID 14259408HCID 14259408, compound

Product 2

HCID 14157744HCID 14157744, compound

HCID 69736117HCID 69736117, compoundYield 64%

Procedure

6-Phenyl-2-hydroxymethyl-tetrahydro-pyran-3,4,5-triol was prepared from 2,3,4,6-tetra-O-acetyl-D-mannopyranosyl bromide according to the method of Hurd and Holysz (Hurd, C. D. and Holysz, R. P., (1950). Reactions of polyacylglycosyl halides with Grignard reagents. J. Am. Chem Soc., 1950, vol 72, 1732-1738) incorporated herein by reference. This compound (2.4 g, 10 mmol) was tritylated, acetylated in the same manner as described for to 2-allyl-6-hydroxymethyl-tetrahydropyran-3,4,5-triol in Example 3 to give acetic acid 4,5-diacetoxy-6-phenyl-2-trityloxymethyl-tetrahydro-pyran-3-yl ester (3.1 g, 64%). This compound was detritylated, phosphorylated and deacetylated as described for acetic acid 4,5-diacetoxy-6-allyl-2-trityloxymethyl-tetrahydropyran-3-yl ester in Example 3 above to give 6-phenyl-3,4,5-trihydroxy-tetrahydro-pyran-2-ylmethyl phosphoric acid ester (22% overall yield) ESMS (−ve) 319 (M−H).