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

HRID 1034483Notes

Reaction equation

HRID 1034483 reaction equation
[N+:1]([C:4]1[CH:44]=[CH:43][C:7]([CH2:8][O:9][C:10]([N:12]2[CH2:16][C@@H:15]([S:17]C(C3C=CC=CC=3)(C3C=CC=CC=3)C3C=CC=CC=3)[CH2:14][C@H:13]2[CH2:37][NH:38][S:39](=[O:42])(=[O:41])[NH2:40])=[O:11])=[CH:6][CH:5]=1)([O-:3])=[O:2].N1C=CC=CC=1>O1CCCC1.O.ClCCl.CO.S.[N+]([O-])([O-])=O.[Ag+]>[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[CH2:37][NH:38][S:39](=[O:41])(=[O:42])[NH2:40])=[O:11])=[CH:43][CH:44]=1)([O-:3])=[O:2]

Participants

9

Reactant 2

HCID 1049PyridineHCID 57161027(2s,4s)-1-p-Nitrobenzyloxycarbonyl-2-sulfamoylaminomethyl-4-tritylthiopyrrolidine

Product 1

HCID 10200398(4-Nitrophenyl)methyl (2S,4S)-2-[[(aminosulfonyl)amino]methyl]-4-mercapto-1-pyrrolidinecarboxylateYield 63%

Reagents, catalysts & solvents 6

HCID 24470Silver NitrateCatalystHCID 402Hydrogen SulfideSolventHCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (2S,4S)-1-p-nitrobenzyloxycarbonyl-2-sulfamoylaminomethyl-4-tritylthiopyrrolidine (668 mg: 0.95 mmole) in tetrahydrofuran (6 ml), a solution of pyridine (0.254 ml: 2.7 eq.) and silver nitrate (403 mg: 2.5 eq.) in water (2 ml) is added under ice cooling. The mixture is stirred at room temperature for 1 hour. The reaction mixture is diluted with dichloromethane (3 ml) and methanol (3 ml), and hydrogen sulfide is bubbled through it under ice cooling for 10 minutes. The resulting precipitate is removed by filtering. The filtrate is diluted with dichloromethane, 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 (233 mg). Yield: 63%. NMR δ(CDCl3 -CD3OD) ppm: 1.42(t, J=7 Hz, 1H), 1.65 to 1.93(m, 1H), 2.48 to 2.70 (m, 1H), 3.05 to 3.63(m, 4H), 3.93 to 4.16(m, 2H), 5.22(s, 2H), 7.53(d, J=8 Hz, 2H), 8.23(d, J=8 Hz, 2H). IR ν (CHCl3) cm-1 : 3276br, 1692, 1607.

Workup

  1. customis bubbled through it under ice cooling for 10 minutes
  2. customThe resulting precipitate is removed
  3. filtrationby filtering
  4. additionThe filtrate is diluted with dichloromethane
  5. washwashed with water
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated in vacuo
  8. customThe residue is purified by silica gel column chromatography (toluene: ethyl acetate)

Sources & evidence

ORD record
ord-0207ada31fd342cf86e23cafffcbd290
Source dataset
uspto-grants-1994_05
Patent number
US05317016

Reaction notes

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