Triethylamine → (2S,4R)-2-(2-hydroxyethyloxymethyl)-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine

HRID 1088972Notes

Reaction equation

HRID 1088972 reaction equation
[C:1]([CH2:4][O:5][CH2:6][C@@H:7]1[CH2:11][C@@H:10]([O:12][S:13]([CH3:16])(=[O:15])=[O:14])[CH2:9][N:8]1[C:17]([O:19][CH2:20][C:21]1[CH:26]=[CH:25][C:24]([N+:27]([O-:29])=[O:28])=[CH:23][CH:22]=1)=[O:18])(O)=[O:2].C(N(CC)CC)C.ClC(OCC(C)C)=O>O1CCCC1>[OH:2][CH2:1][CH2:4][O:5][CH2:6][C@@H:7]1[CH2:11][C@@H:10]([O:12][S:13]([CH3:16])(=[O:15])=[O:14])[CH2:9][N:8]1[C:17]([O:19][CH2:20][C:21]1[CH:22]=[CH:23][C:24]([N+:27]([O-:29])=[O:28])=[CH:25][CH:26]=1)=[O:18]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 62365Isobutyl chloroformateHCID 18631935(2S,4R)-2-(carboxymethyloxymethyl)-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine

Product 1

HCID 18641547(2S,4R)-2-(2-hydroxyethyloxymethyl)-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidineYield 90.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (2S,4R)-2-(carboxymethyloxymethyl)-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (2.4 g) in tetrahydrofuran (50 ml) was added triethyamine (1.6 ml). Isobutyl chloroformate (1.1 ml) was dropwise added to the mixture at -5° to -10° C. under nitrogen, followed by stirring for 30 minutes at the same temperature. The insoluble material was filtered off and the filtrate was added to a solution of sodium borohydride (0.70 g) in water (20 ml) at 0° C. After stirring for 2 hours at the same temperature, acetic acid (3 ml) was added thereto. The reaction mixture was evaporated, diluted with ethyl acetate and washed successively with water, saturated sodium bicarbonate and brine. The dried organic layer was concentrated under reduced pressure, and the obtained syrup was subjected to a column chromatography on silica gel and eluted with a mixture of dichloromethane and acetone (4:1 v/v) to give (2S,4R)-2-(2-hydroxyethyloxymethyl)-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (2.1 g).

Workup

  1. filtrationThe insoluble material was filtered off
  2. additionthe filtrate was added to a solution of sodium borohydride (0.70 g) in water (20 ml) at 0° C
  3. stirringAfter stirring for 2 hours at the same temperature, acetic acid (3 ml)
  4. additionwas added
  5. customThe reaction mixture was evaporated
  6. additiondiluted with ethyl acetate
  7. washwashed successively with water, saturated sodium bicarbonate and brine
  8. concentrationThe dried organic layer was concentrated under reduced pressure
  9. washeluted with a mixture of dichloromethane and acetone (4:1 v/v)

Sources & evidence

ORD record
ord-585be2790640422a8c98bcd74a62c44f
Source dataset
uspto-grants-1990_10
Patent number
US04963543

Reaction notes

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