Benzyl mercaptan → (3R)-3-(Benzylthio)methyl-1-(tert-butoxycarbonyl)pyrrolidine

HRID 1459715Notes

Reaction equation

HRID 1459715 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:12][CH2:11][C@@H:10]([CH2:13]OS(C)(=O)=O)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(=O)([O-])[O-].[K+].[K+].[CH2:25]([SH:32])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1>CN(C=O)C>[CH2:25]([S:32][CH2:13][C@@H:10]1[CH2:11][CH2:12][N:8]([C:6]([O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:7])[CH2:9]1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

5

Reactant 3

HCID 7509Benzyl mercaptanHCID 11430Potassium CarbonateHCID 40479140(R)-tert-butyl 3-(((methylsulfonyl)oxy)methyl)pyrrolidine-1-carboxylate

Product 1

HCID 54246072(3R)-3-(Benzylthio)methyl-1-(tert-butoxycarbonyl)pyrrolidine

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred mixture of (3R)-1-(tert-butoxycarbonyl)-3-[(methane-sulfonyloxy)methyl]pyrrolidine (0.5071 g, 1.82 mmol) and anhydrous potassium carbonate (0.3764 g, 2.72 mmol) in DMF (13 ml), under argon, was added benzyl mercaptan (0.428 ml, 3.65 mmol) and the mixture was stirred overnight at room temperature, then at 60° C. for 4 h. The mixture was then partitioned between water (50 ml) and diethyl ether (30 ml). The aqueous layer was separated and reextracted with more diethyl ether (2×30 ml). The combined organic layers were dried (MgSO4) and evaporated in uacuo. The residue was purified by flash chromatography (silica gel, 20% EtOAc/pet. ether) to give 0.5186 (93%) of the title compound as a colourless oil. δH (360 MHz, CDCl3) 1.45 (9H, s), 1.56 (1H, m), 1.99 (1H, m), 2.32 (1H, m), 2.45 (2H, t, J=6.4 Hz), 2.97 (1H, m), 3.26 (1H, m), 3.61 (2H, m), 3.72 (2H, s), 7.22-7.40 (5H, m). m/e (ES+) 330 (M+Na)+, 308 (M+H)+, 252 (M-CMe3 +2H)+, 234, 213, 208 (M-Boc+2H)+.

Workup

  1. waitat 60° C. for 4 h
  2. customThe mixture was then partitioned between water (50 ml) and diethyl ether (30 ml)
  3. customThe aqueous layer was separated
  4. dry with materialThe combined organic layers were dried (MgSO4)
  5. customevaporated in uacuo
  6. customThe residue was purified by flash chromatography (silica gel, 20% EtOAc/pet. ether)

Sources & evidence

ORD record
ord-cfbdcac36db3474eb55ebb77477dca31
Source dataset
uspto-grants-1998_12
Patent number
US05854268

Reaction notes

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