Hydrochloric Acid → (2S,4S)-4-triphenylmethylthio-2-methoxycarbonyl-1-p-nitrobenzyloxycarbonylpyrrolidine

HRID 2379282Notes

Reaction equation

HRID 2379282 reaction equation
[H-].[Na+].[C:3]1([C:9]([SH:22])([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.CS(O[C@H:28]1[CH2:32][N:31]([C:33]([O:35][CH2:36][C:37]2[CH:42]=[CH:41][C:40]([N+:43]([O-:45])=[O:44])=[CH:39][CH:38]=2)=[O:34])[C@H:30]([C:46]([O:48][CH3:49])=[O:47])[CH2:29]1)(=O)=O.Cl>CN(C)C=O.C(OCC)(=O)C>[C:3]1([C:9]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)([C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)[S:22][C@@H:28]2[CH2:32][N:31]([C:33]([O:35][CH2:36][C:37]3[CH:38]=[CH:39][C:40]([N+:43]([O-:45])=[O:44])=[CH:41][CH:42]=3)=[O:34])[C@H:30]([C:46]([O:48][CH3:49])=[O:47])[CH2:29]2)[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 77281Benzenemethanethiol, alpha,alpha-diphenyl-HCID 57030081(2S,4R)-2-Methyl 1-(4-nitrobenzyl) 4-((methylsulfonyl)oxy)pyrrolidine-1,2-dicarboxylate

Product 1

HCID 57167581(2S,4S)-4-triphenylmethylthio-2-methoxycarbonyl-1-p-nitrobenzyloxycarbonylpyrrolidineYield 59.4%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a suspension of sodium hydride (1.26 g) (60% dispersion in oil) in dimethylformamide (50 ml) under ice cooling is added triphenylmethylmercaptan (10.9 g) in small portions and stirred for 5 minutes at room temperature. A solution of crude (2S,4R)-4-methanesulfonyloxy-2-methoxycarbonyl-1-p-nitrobenzyloxycarbonylpyrrolidine (2:10.6 g) in dimethylformamide (80 ml) is added to this mixture, and the whole mixture is stirred in an oil bath at 50° C. overnight. The reaction mixture is diluted with ethyl acetate and mixed with ice water containing 1N-hydrochloric acid (35 ml). The organic layer is taken, washed with water and satd. brine, dried over sodium sulfate, and concentrated in vacuo. The residue is purified by silica gel chromatography (toluene-ethyl acetate) to give (2S ,4S)-4-triphenylmethylthio-2-methoxycarbonyl-1-p-nitrobenzyloxycarbonylpyrrolidine (3:9.12 g) an orange foam (Yield: 52% from hydroxyproline) and the starting compound (2:3.11 g: Yield: 29%).

Workup

  1. stirringthe whole mixture is stirred in an oil bath at 50° C. overnight
  2. washwashed with water and satd
  3. dry with materialbrine, dried over sodium sulfate
  4. concentrationconcentrated in vacuo
  5. customThe residue is purified by silica gel chromatography (toluene-ethyl acetate)

Sources & evidence

ORD record
ord-4398f05fe32e4d23bab6b806949a3757
Source dataset
uspto-grants-1994_11
Patent number
US05360798

Reaction notes

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