Pyridine → HCID 22851803, compound

HRID 1034477Notes

Reaction equation

HRID 1034477 reaction equation
[CH3:1][O:2][C:3]1[CH:56]=[CH:55][C:6]([CH2:7][O:8][C:9]([N:11]2[CH2:15][C@@H:14]([S:16]C(C3C=CC=CC=3)(C3C=CC=CC=3)C3C=CC=CC=3)[CH2:13][C@H:12]2[CH2:36][NH:37][S:38]([N:41]([C:43]([O:45][CH2:46][C:47]2[CH:52]=[CH:51][C:50]([O:53][CH3:54])=[CH:49][CH:48]=2)=[O:44])[CH3:42])(=[O:40])=[O:39])=[O:10])=[CH:5][CH:4]=1.N1C=CC=CC=1>ClCCl.CO.O.[N+]([O-])([O-])=O.[Ag+]>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]([CH2:7][O:8][C:9]([N:11]2[CH2:15][C@@H:14]([SH:16])[CH2:13][C@H:12]2[CH2:36][NH:37][S:38]([N:41]([C:43]([O:45][CH2:46][C:47]2[CH:48]=[CH:49][C:50]([O:53][CH3:54])=[CH:51][CH:52]=2)=[O:44])[CH3:42])(=[O:39])=[O:40])=[O:10])=[CH:55][CH:56]=1

Participants

7

Reactant 2

HCID 1049PyridineHCID 22851804HCID 22851804, compound

Product 1

HCID 22851803HCID 22851803, compoundYield 83.2%

Reagents, catalysts & solvents 4

HCID 24470Silver NitrateCatalystHCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of (2S,4S)-1-p-methoxybenzyloxycarbonyl-4-tritylthio-2-(N-p-methoxybenzyloxycarbonyl-N-methylaminosulfonyl)aminomethylpyrrolidine (1.5 g: 1.88 mmole) in a mixture of dichloromethane (4 ml) and methanol (10 ml), a solution of pyridine (381 μl: 2.5 eq.) and silver nitrate (640 mg: 2 eq.) in water (6 ml) is added with stirring under ice cooling. The mixture is stirred at the same temperature for 30 minutes. The reaction mixture is diluted with dichloromethane, washed with water, dried over magnesium sulfate, and concentrated in vacuo to about 5 ml. The residue is dissolved in methanol (10 ml) and hydrogen sulfide is bubbled through it. The mixture freed from solid by filtering is concentrated in vacuo. The residue is purified by silica gel column chromatography (toluene:ethyl acetate=2:1) to give (2S,4S)-1-p-methoxybenzyloxycarbonyl-4-mercapto-2-(N-p-methoxybenzyloxycarbonyl-N-methylaminosulfonyl)aminomethylpyrrolidine (866 mg). Yield: 83%. NMR δ(CDCl3) ppm: 1.6 to 1.8(m, 1H), 2.3 to 2.6(m, 1H), 2.9 to 3.4(m, 5H), 3.3(s, 3H), 3.8(s, 6H), 3.8 to 4.2(m, 1H), 6.3 to 6.6(m, 1H), 6.88(d, J=8.6 Hz, 2H), 7.2 to 7.4(m, 2H). IR ν (CHCl3) cm-1 : 1690.

Workup

  1. stirringThe mixture is stirred at the same temperature for 30 minutes
  2. washwashed with water
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated in vacuo to about 5 ml
  5. dissolutionThe residue is dissolved in methanol (10 ml)
  6. customhydrogen sulfide is bubbled through it
  7. filtrationby filtering
  8. concentrationis concentrated in vacuo
  9. customThe residue is purified by silica gel column chromatography (toluene:ethyl acetate=2:1)

Sources & evidence

ORD record
ord-c75df75a122b4b84bca20952c3a07141
Source dataset
uspto-grants-1994_05
Patent number
US05317016

Reaction notes

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