Water → HCID 11793622, compound

HRID 1488294Notes

Reaction equation

HRID 1488294 reaction equation
[CH2:1]([Mg]Br)[CH:2]=[CH2:3].[C:6]([O:9][C@@H:10]1[C@@H:15]([O:16][C:17](=[O:19])[CH3:18])[C@H:14]([O:20][C:21](=[O:23])[CH3:22])[C@@H:13]([CH2:24][O:25][C:26](=[O:28])[CH3:27])[O:12][C@@H:11]1Br)(=[O:8])[CH3:7].O.C(OC(=O)C)(=O)C>CCOCC.N1C=CC=CC=1.C(O)(=O)C>[C:6]([O:9][C@@H:10]1[C@@H:15]([O:16][C:17](=[O:19])[CH3:18])[C@H:14]([O:20][C:21](=[O:23])[CH3:22])[C@@H:13]([CH2:24][O:25][C:26](=[O:28])[CH3:27])[O:12][C@H:11]1[CH2:3][CH:2]=[CH2:1])(=[O:8])[CH3:7]

Participants

8

Reactant 4

HCID 962WaterHCID 7918Acetic AnhydrideHCID 101776alpha-D-Glucopyranosyl bromide, tetraacetateHCID 178455850HCID 178455850, compound

Product 1

HCID 11793622HCID 11793622, compound

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 1049PyridineSolventHCID 3283Diethyl EtherSolvent

Procedure

To a solution of allyl magnesium bromide (100 mL, 100 mmol, 1.0 M in ether,) at 0° C. was added dropwise 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide (4.45 g, 10.82 mmol) in ether (60 mL) over a period of 1 hr. After completion of the addition, the mixture was allowed to warm up and stirred at rt overnight. To the resulting mixture was carefully added water (200 mL) and followed by the addition of acetic acid to dissolve magnesium salts. Th organic layer was separated and concentrated. The residue was treated with acetic anhydride (70 mL, 740 mmol) and pyridine (100 mL). After stirring at rt overnight, the mixture was concentrated and the residue taken up in EtOAc (200 mL) and washed with sat'd NaHCO3 (5×300 mL), dried over MgSO4, filtered and evaporated. The residue was purified by flash chromatography on silica gel (120 g, eluting with 0-100% EtOAc in hexanes) to give the title compound. 1H NMR (CDCl3) δ 2.00 (s, 3H), 2.03 (s, 3H), 2.04 (s, 3H), 2.09 (s, 3H), 2.26-2.37 (m, 2H), 3.51 (m, 1H), 3.65 (m, 1H), 4.10 (dd, J=12.2, 2.2, 1H), 4.24 (dd, J=12.2, 5.0, 1H), 4.93 (t, J=9.4, 1H), 5.07 (m, 2H), 5.09 (s, 1H), 5.17 (t, J=9.4, 1H), 5.83 (m, 1H).

Workup

  1. additionAfter completion of the addition
  2. temperatureto warm up
  3. customTh organic layer was separated
  4. concentrationconcentrated
  5. stirringAfter stirring at rt overnight
  6. concentrationthe mixture was concentrated
  7. washwashed with sat'd NaHCO3 (5×300 mL)
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customevaporated
  11. customThe residue was purified by flash chromatography on silica gel (120 g, eluting with 0-100% EtOAc in hexanes)

Sources & evidence

ORD record
ord-743e7c82f3784b21845e835f776b1869
Source dataset
uspto-grants-2016_08
Patent number
US09427475B2

Reaction notes

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