1-Methylimidazole → (3R*,4R*)-3,4-epoxy-6-methoxy-2,2-dimethyl-7-nitro-3,4-dihydro-2H-1-benzopyran

HRID 2425356Notes

Reaction equation

HRID 2425356 reaction equation
[CH3:1][O:2][C:3]1[C:4]([N+:15]([O-:17])=[O:16])=[CH:5][C:6]2[O:11][C:10]([CH3:13])([CH3:12])[CH:9]=[CH:8][C:7]=2[CH:14]=1.CN1C=CN=C1.I(C1C=CC=CC=1)=[O:25].S([O-])([O-])(=O)=S.[Na+].[Na+]>C(#N)C>[O:25]1[C@H:8]2[C@@H:9]1[C:10]([CH3:13])([CH3:12])[O:11][C:6]1[CH:5]=[C:4]([N+:15]([O-:17])=[O:16])[C:3]([O:2][CH3:1])=[CH:14][C:7]=12

Participants

6

Reactant 4

HCID 13901-MethylimidazoleHCID 24477Sodium ThiosulfateHCID 92125IodosylbenzeneHCID 591343256-methoxy-2,2-dimethyl-7-nitro-2H-1-benzopyran

Product 1

HCID 25196994(3R*,4R*)-3,4-epoxy-6-methoxy-2,2-dimethyl-7-nitro-3,4-dihydro-2H-1-benzopyranYield 75%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution (300 mL) of acetonitrile containing 6-methoxy-2,2-dimethyl-7-nitro-2H-1-benzopyran (10.0 g, 42.5 mmol), N-methyl imidazole (0.678 mL, 8.50 mmol), (R,R,S,S)-Ph,Ph salen manganese complex (XX) (880 mg, 0.850 mmol) and iodosobenzene (18.7 mg, 85.0 mmol) were added at room temperature and the mixture was stirred for 2 hours. Upon the completion of the reaction, an aqueous solution of sodium thiosulfate was added to the reaction solution, the resulting solution was filtered through celite. The resulting filtrate extracted with ethyl acetate. The organic phase was washed with water and sodium chloride solution, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by column chromatography (hexane/ethyl acetate=4/1) and the aimed product was obtained as yellow crystal (yield: 75%, optical purity: 99.7% ee).

Workup

  1. additionwere added at room temperature
  2. customUpon the completion of the reaction
  3. filtrationthe resulting solution was filtered through celite
  4. extractionThe resulting filtrate extracted with ethyl acetate
  5. washThe organic phase was washed with water and sodium chloride solution
  6. dry with materialdried over anhydrous magnesium sulfate
  7. distillationAfter distilling off the solvent
  8. customthe residue was purified by column chromatography (hexane/ethyl acetate=4/1)

Sources & evidence

ORD record
ord-0aba5c544c794c2398a5e16ced2edbe0
Source dataset
uspto-grants-2011_06
Patent number
US07964623B2

Reaction notes

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