Potassium Carbonate → HCID 78015405, compound

HRID 1497277Notes

Reaction equation

HRID 1497277 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@H:14]2[NH:15][C:16](=[O:18])[O:17][C@H:13]2[CH2:12][C@H:11]([CH2:19][O:20]CC2C=CC=CC=2)[C@H:10]1[O:28][CH2:29][C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([O-])([O-])=O.[K+].[K+]>C(OC(=O)C)(=O)C.C(O)(=O)C.CO.[Cl-].[Cl-].[Zn+2]>[CH2:1]([O:8][CH:9]1[CH:14]2[NH:15][C:16](=[O:18])[O:17][CH:13]2[CH2:12][CH:11]([CH2:19][OH:20])[CH:10]1[O:28][CH2:29][C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 2

HCID 11430Potassium CarbonateHCID 67480430HCID 67480430, compound

Product 1

HCID 78015405HCID 78015405, compoundYield 77%

Reagents, catalysts & solvents 4

HCID 3007855ZincchlorideCatalystHCID 176Acetic AcidSolventHCID 887MethanolSolventHCID 7918Acetic AnhydrideSolvent

Procedure

To a solution of (3aS,4R,5R,6R,7aS)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)hexahydrobenzo[d]oxazol-2(3H)-one (3.00 g, 6.34 mmol) in acetic anhydride (60 mL) and acetic acid (10 mL) was added anhydrous ZnCl2 (8.62 g, 63.4 mmol). The mixture was stirred at room temperature for 3 h. Most of the solvents were removed by evaporation under high vacuum. The residue was diluted with aqueous saturated NaHCO3 (200 mL) and extracted with EtOAc (2×50 mL). The extracts were washed with brine, dried with MgSO4. The solvent was evaporated to give white foam. This was dissolved in MeOH (50 mL) and K2CO3 (1.75 g, 12.7 mmol) was added. The mixture was stirred at room temperature for 2 h. Solvent was evaporated. The residue was diluted with water (50 mL) and extracted with DCM (2×30 mL). The extracts were washed with brine, dried with MgSO4. The solvent was evaporated to give white foam which was purified by a silica gel column, eluting with 5% MeOH in DCM to give 3aS,4R,5R,6R,7aS)-4,5-bis(benzyloxy)-6-(hydroxymethyl)hexahydrobenzo[d]oxazol-2(3H)-one as a white solid (1.86 g, 77%). 1H NMR (400 MHz, CDCl3) δ 7.33-7.42 (m, 10H), 4.95 (d, J=11.8 Hz, 1H), 4.89 (d, J=10.9 Hz, 1H), 4.82 (s, 1H), 4.69 (d, J=11.3 Hz, 1H), 4.64-4.69 (m, 1H), 4.60 (d, J=11.8 Hz, 1H), 3.72-3.77 (m, 1H), 3.50-3.56 (m, 3H), 3.40 (t, J=9.1 Hz, 1H), 2.12 (dt, J=15.3 Hz, 3.1 Hz, 1H), 1.91-1.98 (m, 1H), 1.69-1.77 (m, 1H), 1.55 (t, J=4.9 Hz, 1H).

Workup

  1. customMost of the solvents were removed by evaporation under high vacuum
  2. additionThe residue was diluted with aqueous saturated NaHCO3 (200 mL)
  3. extractionextracted with EtOAc (2×50 mL)
  4. washThe extracts were washed with brine
  5. dry with materialdried with MgSO4
  6. customThe solvent was evaporated
  7. customto give white foam
  8. stirringThe mixture was stirred at room temperature for 2 h
  9. customSolvent was evaporated
  10. additionThe residue was diluted with water (50 mL)
  11. extractionextracted with DCM (2×30 mL)
  12. washThe extracts were washed with brine
  13. dry with materialdried with MgSO4
  14. customThe solvent was evaporated
  15. customto give white foam which
  16. customwas purified by a silica gel column
  17. washeluting with 5% MeOH in DCM

Sources & evidence

ORD record
ord-2c15d1cb75be48f6a128c8845aec90ea
Source dataset
uspto-grants-2015_12
Patent number
US09199949B2

Reaction notes

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