Pyridine → (2S,4S)-4-mercapto-2-acetylaminooxymethyl-1-p-nitrobenzyloxycarbonylpyrrolidine

HRID 260001Notes

Reaction equation

HRID 260001 reaction equation
C([S:20][C@@H:21]1[CH2:25][N:24]([C:26]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][C:33]([N+:36]([O-:38])=[O:37])=[CH:32][CH:31]=2)=[O:27])[C@H:23]([CH2:39][O:40][NH:41][C:42](=[O:44])[CH3:43])[CH2:22]1)(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.N1C=CC=CC=1>CO.O.[N+]([O-])([O-])=O.[Ag+]>[SH:20][C@@H:21]1[CH2:25][N:24]([C:26]([O:28][CH2:29][C:30]2[CH:31]=[CH:32][C:33]([N+:36]([O-:38])=[O:37])=[CH:34][CH:35]=2)=[O:27])[C@H:23]([CH2:39][O:40][NH:41][C:42](=[O:44])[CH3:43])[CH2:22]1

Participants

6

Reactant 2

HCID 1049PyridineHCID 15814452HCID 15814452, compound

Product 1

HCID 15814453(2S,4S)-4-mercapto-2-acetylaminooxymethyl-1-p-nitrobenzyloxycarbonylpyrrolidineYield 73%

Reagents, catalysts & solvents 3

HCID 24470Silver NitrateCatalystHCID 887MethanolSolvent2×HCID 962WaterSolvent

Procedure

To a solution of (2S,4S)-4-tritylthio-2-acetylaminooxymethyl-1-p-nitrobenzyloxycarbonylpyrrolidine (7a: 452 mg) in methanol (9 ml) under ice cooling are dropwise added pyridine (149 μl) and then a solution of silver nitrate (289 mg) in a mixture of water (1.5 ml) and methanol (15 ml), and the mixture is stirred for 25 minutes. Separating silver salt is collected by filtration, washed with methanol, ether, and petroleum ether, and dried. To a suspension of this crude silver salt in a mixture of dichloromethane (3.5 ml) and methanol (3.5 ml) is introduced hydrogen sulfide gas for 5 minutes. The resulting silver sulfide is filtered off and washed with a mixture of methanol and dichloromethane. The filtrate is concentrated in vacuo. The residue is purified by silica gel chromatography to give (2S,4S)-4-mercapto-2-acetylaminooxymethyl-1-p-nitrobenzyloxycarbonylpyrrolidine (8a: 198 mg) as a pale yellow foam. Yield: 73%.

Workup

  1. filtrationSeparating silver salt is collected by filtration
  2. washwashed with methanol, ether, and petroleum ether
  3. customdried
  4. additionTo a suspension of this crude silver salt
  5. additionin a mixture of dichloromethane (3.5 ml) and methanol (3.5 ml)
  6. additionis introduced hydrogen sulfide gas for 5 minutes
  7. filtrationThe resulting silver sulfide is filtered off
  8. washwashed with a mixture of methanol and dichloromethane
  9. concentrationThe filtrate is concentrated in vacuo
  10. customThe residue is purified by silica gel chromatography

Sources & evidence

ORD record
ord-d5f417db1e9949fd85e9357460cb768d
Source dataset
uspto-grants-1996_06
Patent number
US05523415

Reaction notes

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