Dimethylformamide → 4-Methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine

HRID 37276Notes

Reaction equation

HRID 37276 reaction equation
CN(C)C=O.P(Cl)(Cl)(Cl)=O.C(C1N=C([C@@H:19]2[CH2:23][C@@H:22]([O:24][S:25]([CH3:28])(=[O:27])=[O:26])[CH2:21][N:20]2[C:29]([O:31][CH2:32][C:33]2[CH:38]=[CH:37][C:36]([N+:39]([O-:41])=[O:40])=[CH:35][CH:34]=2)=[O:30])SC=1)(O)=O.O.N>O1CCCC1>[CH3:28][S:25]([O:24][CH:22]1[CH2:21][N:20]([C:29]([O:31][CH2:32][C:33]2[CH:38]=[CH:37][C:36]([N+:39]([O-:41])=[O:40])=[CH:35][CH:34]=2)=[O:30])[CH2:19][CH2:23]1)(=[O:26])=[O:27]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 24813Phosphorus oxychlorideHCID 12896473Azane;hydrateHCID 18638791(2S,4R)-2-(4-carboxythiazol-2-yl)-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl) pyrrolidine

Product 1

HCID 222428884-Methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidineYield 124.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a mixture of dimethylformamide (0.45 ml) and tetrahydrofuran (10 ml) was dropwise added phosphorus oxychloride (0.46 ml) at -5°∫5° C., and the mixture was stirred at the same temperature for 30 minutes. To the mixture was added a solution of (2S,4R)-2-(4-carboxythiazol-2-yl) -4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl) pyrrolidine (1.54 g) in tetrahydrofuran (20 ml) at -5°∫5° C., followed by stirring at the same temperature for 30 minutes. The mixture was dropwise added to concentrated ammonia water (15 ml) at 0°-10° C. with stirring. The mixture was stirred at the same condition for 2 hours. Tetrahydrofuran was removed under reduced pressure to give a residue, which was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give (2S, 4R)-2-(4-carbamoylthiazol)-2-yl) -4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (1.4 g).

Workup

  1. customat -5°
  2. custom∫5° C.
  3. stirringby stirring at the same temperature for 30 minutes
  4. stirringwith stirring
  5. stirringThe mixture was stirred at the same condition for 2 hours
  6. customTetrahydrofuran was removed under reduced pressure
  7. customto give a residue, which
  8. extractionwas extracted with ethyl acetate
  9. dry with materialThe organic layer was dried over magnesium sulfate
  10. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-e47ef4e0559c40acb2ec7e2e9b0dc4e6
Source dataset
uspto-grants-1995_05
Patent number
US05420122

Reaction notes

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