Dimethyl Sulfoxide → 1,1-Dimethylethyl (2S,4R)-2-formyl-4-[(methylsulfonyl)oxy]-1-pyrrolidinecarboxylate

HRID 324697Notes

Reaction equation

HRID 324697 reaction equation
CS(C)=O.C(Cl)(=O)C(Cl)=O.[C:11]([O:15][C:16]([N:18]1[CH2:22][C@H:21]([O:23][S:24]([CH3:27])(=[O:26])=[O:25])[CH2:20][C@H:19]1[CH2:28][OH:29])=[O:17])([CH3:14])([CH3:13])[CH3:12].C(N(CC)CC)C>C(Cl)Cl.O>[C:11]([O:15][C:16]([N:18]1[CH2:22][C@H:21]([O:23][S:24]([CH3:27])(=[O:25])=[O:26])[CH2:20][C@H:19]1[CH:28]=[O:29])=[O:17])([CH3:14])([CH3:13])[CH3:12]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 10589967HCID 10589967, compound

Product 1

HCID 572075911,1-Dimethylethyl (2S,4R)-2-formyl-4-[(methylsulfonyl)oxy]-1-pyrrolidinecarboxylateYield 93.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent3×

Procedure

A solution of dimethyl sulfoxide (4.2 ml, 59.3 mM) in anhydrous methylene chloride(20 ml) was added dropwise into a solution of oxalyl chloride (3.5 ml, 40.3 mM) in anhydrous methylene chloride (100 ml) at −70 ° C. in a nitrogen gas stream and the mixture was stirred for 20 minutes. A solution of (2S,4R)-N-tert-butoxycarbonyl-4-methanesulfonyloxy-2-hydorxymethylpyrrolidine (7 g, 23.7 mM) in anhydrous methylene chloride (20 ml) was added dropwise and the mixture was further stirred for 20 minutes. After adding dropwise triethylamine (11.6 ml, 83.0 mM) thereto, the mixture was warmed up to room temperature. The reaction mixture was poured into water and the organic layer was washed with a 10% aqueous solution of citric acid, water, a saturated aqueous solution of sodium carbonate and brine in this order and dried over anhydrous magnesium sulfate. After removing the solvent, the resulting solid matter was washed with hexane to give the title compound (6.5 g, 93%).

Workup

  1. stirringthe mixture was further stirred for 20 minutes
  2. washthe organic layer was washed with a 10% aqueous solution of citric acid, water
  3. dry with materiala saturated aqueous solution of sodium carbonate and brine in this order and dried over anhydrous magnesium sulfate
  4. customAfter removing the solvent
  5. washthe resulting solid matter was washed with hexane

Sources & evidence

ORD record
ord-24170d8ca8b04319936fe092ac5c7a82
Source dataset
uspto-grants-2001_04
Patent number
US06218550B1

Reaction notes

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