Ammonium Chloride → (R)-4-((2R,4R,6R)-4-Amino-2-methoxy-6-(pent-4-enyl)-tetrahydro-2H-pyran-2-yl)-3-(4-methoxybenzyl)thiazolidin-2-one

HRID 2251793Notes

Reaction equation

HRID 2251793 reaction equation
[N:1]([C@@H:4]1[CH2:9][C@@H:8]([CH2:10][CH2:11][CH2:12][CH:13]=[CH2:14])[O:7][C@:6]([C@@H:17]2[CH2:21][S:20][C:19](=[O:22])[N:18]2[CH2:23][C:24]2[CH:29]=[CH:28][C:27]([O:30][CH3:31])=[CH:26][CH:25]=2)([O:15][CH3:16])[CH2:5]1)=[N+]=[N-].[NH4+].[Cl-]>C(O)C.O.C(OCC)(=O)C.[Zn]>[NH2:1][C@@H:4]1[CH2:9][C@@H:8]([CH2:10][CH2:11][CH2:12][CH:13]=[CH2:14])[O:7][C@:6]([C@@H:17]2[CH2:21][S:20][C:19](=[O:22])[N:18]2[CH2:23][C:24]2[CH:29]=[CH:28][C:27]([O:30][CH3:31])=[CH:26][CH:25]=2)([O:15][CH3:16])[CH2:5]1

Participants

7

Reactant 2

HCID 25517Ammonium Chloride3×HCID 59644060(R)-4-((2R,4R,6R)-4-Azido-2-methoxy-6-(pent-4-enyl)-tetrahydro-2H-pyran-2-yl)-3-(4-methoxybenzyl)thiazolidin-2-one

Product 1

HCID 59644046(R)-4-((2R,4R,6R)-4-Amino-2-methoxy-6-(pent-4-enyl)-tetrahydro-2H-pyran-2-yl)-3-(4-methoxybenzyl)thiazolidin-2-oneYield 75%

Reagents, catalysts & solvents 4

HCID 23994ZincCatalyst3×HCID 702EthanolSolvent2×HCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A suspension of the title compound from Example 66 (432 mg, 0.967 mmol) in ethanol (3 mL) and water (1 mL) was treated with NH4Cl (122 mg, 2.27 mmol) and zinc dust (85.4 mg, 1.30 mmol), and the mixture was stirred vigorously at room temperature. After 6 h, an additional portion of zinc (100 mg) and NH4Cl (127 mg) was added, together with additional ethanol (4.5 mL) and water (1.5 mL), and stirring was continued for 18 h. Once more portions of zinc (100 mg) and NH4Cl (124 mg) were added, and stirring was continued. After 4 h, the mixture was diluted with ethyl acetate, washed with half-concentrated NH4OH and brine, dried, and concentrated. The residue was treated with NH4Cl (200 mg) in methanol (20 mL), and this mixture was allowed to stir at room temperature for 2 days. The mixture was diluted with ethyl acetate, washed with 1/1-satd aq NaHCO3/brine and then with brine, dried, and concentrated. Chromatography of the residue on silica gel eluting with methanol/dichloromethane gave the title compound (305 mg, 75%) as an oil.

Workup

  1. stirringstirring
  2. waitwas continued for 18 h
  3. stirringstirring
  4. waitAfter 4 h
  5. washwashed with half-concentrated NH4OH and brine
  6. customdried
  7. concentrationconcentrated
  8. additionThe residue was treated with NH4Cl (200 mg) in methanol (20 mL)
  9. stirringto stir at room temperature for 2 days
  10. additionThe mixture was diluted with ethyl acetate
  11. washwashed with 1/1-satd aq NaHCO3/brine
  12. dry with materialwith brine, dried
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-ce8b72b931de40f9a0dd4ca53fca9840
Source dataset
uspto-grants-2008_01
Patent number
US07320974B2

Reaction notes

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