Hydrochloric Acid → (2S,4S)-allyl 2-(((allyloxycarbonyl)(sulfamoyl)amino)methyl)-4-mercaptopyrrolidine-1-carboxylate

HRID 1034531Notes

Reaction equation

HRID 1034531 reaction equation
C([S:4][C@@H:5]1[CH2:9][N:8]([C:10]([O:12][CH2:13][CH:14]=[CH2:15])=[O:11])[C@H:7]([CH2:16][N:17]([S:24](=[O:27])(=[O:26])[NH2:25])[C:18]([O:20][CH2:21][CH:22]=[CH2:23])=[O:19])[CH2:6]1)(=O)C.C[O-].[Na+].CO.Cl>C1(C)C=CC=CC=1.O>[CH2:13]([O:12][C:10]([N:8]1[CH2:9][C@@H:5]([SH:4])[CH2:6][C@H:7]1[CH2:16][N:17]([S:24](=[O:26])(=[O:27])[NH2:25])[C:18]([O:20][CH2:21][CH:22]=[CH2:23])=[O:19])=[O:11])[CH:14]=[CH2:15]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 887MethanolHCID 10942334Sodium MethoxideHCID 57143963(2S,4S)-4-acetylthio-1-allyloxycarbonyl-2-(N-sulfamoyl-N-allyloxycarbonylamino)methylpyrrolidine

Product 1

HCID 57114535(2S,4S)-allyl 2-(((allyloxycarbonyl)(sulfamoyl)amino)methyl)-4-mercaptopyrrolidine-1-carboxylateYield 78.6%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent2×

Procedure

To a solution of (2S,4S)-4-acetylthio-1-allyloxycarbonyl-2-(N-sulfamoyl-N-allyloxycarbonylamino)methylpyrrolidine (6.70 g: 16.4 mmole) in toluene (50 ml), 4.92M solution of sodium methoxide in methanol (5.0 ml: 24.7 mmole) is added at -30° C. The mixture is stirred for 30 minutes, and diluted with water (55 ml). The aqueous layer is taken, diluted with toluene (50 ml), acidified with concentrated hydrochloric acid (2.3 ml) under ice cooling, and stirred. The organic layer is taken, successively washed with water and saturated brine, dried over magnesium sulfate and concentrated in vacuo. The residual oil is purified by silica gel chromatography (toluene-ethyl acetate) to give (2S,4S)-1-allyloxycarbonyl-2-(N-sulfamoyl-N-allyloxycarbonylamino)methyl-4-mercaptopyrrolidine (4.89 g). Yield: 78%. Colorless oil. NMR δ(CDCl3) ppm: 1.5 to 1.7(m, 1H), 2.35(s, 3H), 2.5 to 2.7(m, 1H), 3.19(dd, J=6.3 Hz, J=11.5 Hz, 1H), 3.68(dd, J=3.8 Hz, J=14.5 Hz, 1H), 3.9 to 4.3(m, 3H), 4.3 to 4.7(m, 5H), 5.2 to 5.4(m, 4H), 5.8 to 6.1(m, 4H). IR ν (CHCl3) cm-1 : 1718, 1684, 1179, 1160.

Workup

  1. stirringstirred
  2. washsuccessively washed with water and saturated brine
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated in vacuo
  5. customThe residual oil is purified by silica gel chromatography (toluene-ethyl acetate)

Sources & evidence

ORD record
ord-b5da3e9b07a6484d9a33b326840d4615
Source dataset
uspto-grants-1994_05
Patent number
US05317016

Reaction notes

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