Sodium methanesulfinate → HCID 66727614, compound

HRID 2198231Notes

Reaction equation

HRID 2198231 reaction equation
Br[C:2]1[CH:7]=[C:6]([C@@H:8]([NH:10][S:11]([C:13]([CH3:16])([CH3:15])[CH3:14])=[O:12])[CH3:9])[CH:5]=[CH:4][N:3]=1.[CH3:17][S:18]([O-:20])=[O:19].[Na+]>CS(C)=O.[NH4+].[Cl-].C([O-])(O)=O.[Na+].CCOC(C)=O.[Cu]I>[CH3:17][S:18]([C:2]1[CH:7]=[C:6]([C@@H:8]([NH:10][S:11]([C:13]([CH3:16])([CH3:15])[CH3:14])=[O:12])[CH3:9])[CH:5]=[CH:4][N:3]=1)(=[O:20])=[O:19]

Participants

8

Reactant 2

HCID 2733271Sodium methanesulfinateHCID 86640807HCID 86640807, compound

Product 1

HCID 66727614HCID 66727614, compound

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 679Dimethyl SulfoxideSolventHCID 8857Ethyl AcetateSolventHCID 25517Ammonium ChlorideSolventHCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
130 °C

Procedure

To a solution of 2-methyl-propane-2-sulfinic acid [(S)-1-(2-bromo-pyridin-4-yl)-ethyl]-amide (3.10 g, 10.2 mmol) (containing 5 wt % of the other diastereomer) in DMSO (120 mL) was added sodium methanesulfinate (3.7 g, 31 mmol) and copper (I) iodide (5.8 g, 31 mmol) The mixture was warmed at 130° C. for 45 minutes. The reaction was diluted with saturated aqueous NH4Cl (90 mL), saturated aqueous NaHCO3 (10 mL), and EtOAc (150 mL), and sonicated for 10 minutes to dissolve all the solids. The aqueous phase was separated and the organic layer was washed with a mixture of saturated aqueous NH4Cl (90 mL) in saturated aqueous NaHCO3 (10 mL). The combined aqueous layers were extracted with EtOAc (150 mL). The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated. The crude material was purified by silica gel chromatography eluting with a gradient of 75-100% EtOAc in hexanes to afford 2-methyl-propane-2-sulfinic acid [(S)-1-(2-methanesulfonyl-pyridin-4-yl)-ethyl]-amide as a clear thick oil as a single diastereomer.

Workup

  1. customsonicated for 10 minutes
  2. dissolutionto dissolve all the solids
  3. customThe aqueous phase was separated
  4. washthe organic layer was washed with a mixture of saturated aqueous NH4Cl (90 mL) in saturated aqueous NaHCO3 (10 mL)
  5. extractionThe combined aqueous layers were extracted with EtOAc (150 mL)
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude material was purified by silica gel chromatography
  11. washeluting with a gradient of 75-100% EtOAc in hexanes

Sources & evidence

ORD record
ord-e8ded806591a41478dd9c502862c413a
Source dataset
uspto-grants-2012_12
Patent number
US08338610B2

Reaction notes

Loading…