Sodium methanesulfinate → HCID 66727614, compound

HRID 1423054Notes

Reaction equation

HRID 1423054 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-bromopyridin-4-yl)-ethyl]-amide (3.10 g, 10.2 mmol) (containing 5 wt % of the other diastereomer) in DMSO (120 mL) is added sodium methanesulfinate (3.7 g, 31 mmol) and copper (I) iodide (5.8 g, 31 mmol). The mixture is warmed at 130° C. for 45 minutes. The reaction is 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 is separated and the organic layer is washed with a mixture of saturated aqueous NH4Cl (90 mL) in saturated aqueous NaHCO3 (10 mL). The combined aqueous layers are extracted with EtOAc (150 mL). The combined organic layers are washed with brine, dried over sodium sulfate, filtered and concentrated. The crude material is 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 an oil as a single diastereomer.

Workup

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

Sources & evidence

ORD record
ord-979012434b5245c8b234066c5a8f5c22
Source dataset
uspto-grants-2015_01
Patent number
US08927550B2

Reaction notes

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