Ammonia → (2R,4S)-1-(p-nitrobenzyloxycarbonyl)-2-aminocarbonylmethyl-4-acetylthiopyrrolidine

HRID 1088260Notes

Reaction equation

HRID 1088260 reaction equation
[N+:1]([C:4]1[CH:26]=[CH:25][C:7]([CH2:8][O:9][C:10]([N:12]2[CH2:16][C@@H:15]([S:17][C:18](=[O:20])[CH3:19])[CH2:14][C@H:13]2[CH2:21][C:22]([OH:24])=O)=[O:11])=[CH:6][CH:5]=1)([O-:3])=[O:2].ClC(OCC)=O.[NH3:33].Cl>O1CCCC1.C(OCC)(=O)C.C(N(CC)CC)C>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([CH2:8][O:9][C:10]([N:12]2[CH2:16][C@@H:15]([S:17][C:18](=[O:20])[CH3:19])[CH2:14][C@H:13]2[CH2:21][C:22]([NH2:33])=[O:24])=[O:11])=[CH:25][CH:26]=1)([O-:3])=[O:2]

Participants

8

Reactant 4

HCID 222AmmoniaHCID 313Hydrochloric AcidHCID 10928Ethyl chloroformateHCID 14830201(2R,4S)-1-(p-Nitrobenzyloxycarbonyl)-2-carboxymethyl-4-acetylthiopyrrolidine

Product 1

HCID 15671452(2R,4S)-1-(p-nitrobenzyloxycarbonyl)-2-aminocarbonylmethyl-4-acetylthiopyrrolidine

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolvent

Procedure

(2R,4S)-1-(p-Nitrobenzyloxycarbonyl)-2-carboxymethyl-4-acetylthiopyrrolidine (82 mg) was dissolved in 1.5 ml of dry tetrahydrofuran, and 33 mg of triethylamine was added thereto. Ethyl chloroformate (35 mg) was added to the mixture under nitrogen stream at -10° to -15° C., followed by stirring at the same temperature for 30 minutes. 29% (w/w) Aqueous ammonia (13 mg) was added at -40° C. to the resulting mixture, followed by stirring at -30° to -40° C. for 30 minutes. The reaction mixture was acidified with dilute hydrochloric acid, diluted with ethyl acetate, washed successively with water, a saturated sodium bicarbonate solution and water, dried over anhydrous sodium sulfate and distilled to remove the solvent. The residue was purified by silica gel thin layer chromatography to obtain (2R,4S)-1-(p-nitrobenzyloxycarbonyl)-2-aminocarbonylmethyl-4-acetylthiopyrrolidine.

Workup

  1. stirringby stirring at -30° to -40° C. for 30 minutes
  2. washwashed successively with water
  3. dry with materiala saturated sodium bicarbonate solution and water, dried over anhydrous sodium sulfate
  4. distillationdistilled
  5. customto remove the solvent
  6. customThe residue was purified by silica gel thin layer chromatography

Sources & evidence

ORD record
ord-f29894d0e36e41aea28a896c9fe03a87
Source dataset
uspto-grants-1990_10
Patent number
US04962103

Reaction notes

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