Hydrochloric Acid → (4-Nitrophenyl)methyl (2S,4S)-2-[[(aminosulfonyl)amino]methyl]-4-mercapto-1-pyrrolidinecarboxylate

HRID 1941582Notes

Reaction equation

HRID 1941582 reaction equation
[N+:1]([C:4]1[CH:21]=[CH:20][C:7]([CH2:8][O:9][C:10]([N:12]2[CH2:16][C@@H:15]([SH:17])[CH2:14][C@H:13]2[CH2:18][NH2:19])=[O:11])=[CH:6][CH:5]=1)([O-:3])=[O:2].C(N(CC)CC)C.C[Si](C)(C)Cl.[S:34](Cl)(=[O:37])(=[O:36])[NH2:35].Cl>ClCCl>[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]([SH:17])[CH2:14][C@H:13]2[CH2:18][NH:19][S:34](=[O:37])(=[O:36])[NH2:35])=[O:11])=[CH:20][CH:21]=1)([O-:3])=[O:2]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 6397ChlorotrimethylsilaneHCID 8471Triethylamine2×HCID 24499Chlorosulfamic acidHCID 57083137(2s,4s)-1-p-Nitrobenzyloxycarbonyl-2-aminomethyl-4-mercaptopyrrolidine

Product 1

HCID 10200398(4-Nitrophenyl)methyl (2S,4S)-2-[[(aminosulfonyl)amino]methyl]-4-mercapto-1-pyrrolidinecarboxylateYield 66.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of crude (2S,4S)-1-p-nitrobenzyloxycarbonyl-2-aminomethyl-4-mercaptopyrrolidine (3.3 g: 10.18 mmole) in dichloromethane (100 ml) at -78° C., triethylamine (2.84 ml: 2.2 eq.) and trimethylchlorosilane (3.12 ml: 2.2 eq.) are dropwise added. After stirring for 20 minutes, triethylamine (4.25 ml: 3 eq.) and 1M-sulfamoyl chloride in dichloromethane (25 ml: 2.5 eq.) are dropwise added to the mixture. After 20 minutes stirring, the reaction mixture is acidified with hydrochloric acid, warmed to room temperature, and extracted with dichloromethane. The extract is washed with water, and 1N-hydrochloric acid (10 ml) and methanol (30 ml) are added thereto. The solution is stirred at room temperature for 30 minutes. The reaction mixture is washed with water, dried over magnesium sulfate, and concentrated in vacuo. The residue is purified by silica gel column chromatography (toluene: ethyl acetate) to give (2S,4S)-1-p-nitrobenzyloxycarbonyl-2-sulfamoylaminomethyl-4-mercaptopyrrolidine (2.65 g). Yield: 66.7%.

Workup

  1. stirringAfter 20 minutes stirring
  2. extractionextracted with dichloromethane
  3. washThe extract is washed with water, and 1N-hydrochloric acid (10 ml) and methanol (30 ml)
  4. additionare added
  5. stirringThe solution is stirred at room temperature for 30 minutes
  6. washThe reaction mixture is washed with water
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. customThe residue is purified by silica gel column chromatography (toluene: ethyl acetate)

Sources & evidence

ORD record
ord-463d0b6d24614151a9f174d7121744b0
Source dataset
uspto-grants-1997_12
Patent number
US05703243

Reaction notes

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