N-Fluorobenzenesulfonimide → Methyl 2-[2-(2,2-dimethylpropyl)benzoxazol-5-yl]-2-fluoropropionate

HRID 48174Notes

Reaction equation

HRID 48174 reaction equation
C([N-]C(C)C)(C)C.[Li+].[CH3:9][C:10]([CH3:28])([CH3:27])[CH2:11][C:12]1[O:13][C:14]2[CH:20]=[CH:19][C:18]([CH:21]([CH3:26])[C:22]([O:24][CH3:25])=[O:23])=[CH:17][C:15]=2[N:16]=1.C1C=CC(S(N(S(C2C=CC=CC=2)(=O)=O)[F:39])(=O)=O)=CC=1>O1CCCC1>[CH3:9][C:10]([CH3:27])([CH3:28])[CH2:11][C:12]1[O:13][C:14]2[CH:20]=[CH:19][C:18]([C:21]([F:39])([CH3:26])[C:22]([O:24][CH3:25])=[O:23])=[CH:17][C:15]=2[N:16]=1

Participants

5

Reactant 3

HCID 588007N-FluorobenzenesulfonimideHCID 2724682Lithium diisopropylamideHCID 22742115HCID 22742115, compound

Product 1

HCID 22742109Methyl 2-[2-(2,2-dimethylpropyl)benzoxazol-5-yl]-2-fluoropropionateYield 78%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

A solution of lithium diisopropylamide (2.0M solution in tetrahydrofuran/ethylbenzene/heptane, 4.55 ml, 0.009 mol) was added, dropwise, to a solution of methyl 2-[2-(2,2-dimethylpropyl)benzoxazol-5-yl]propionate (2.5 g, 0.009 mol) in tetrahydrofran (65 ml) at −70° C. under a nitrogen atmosphere and the mixture was stirred at −70° C. for 1 hour. A solution of N-fluorobenzensulfonimide (2.9 g. 0.009 mol) in tetrahydrofuran (15 ml) was added and the mixture was stirred at −70° C. for a further 1 hour. The cooling bath was removed and the reaction mixture was allowed to warm to room temperature, with stirring over 1½ hours. The mixture was quenched with water, acidified with dilute aqueous hydrochloric acid and extracted with ethyl acetate. The organic extract was washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with ethyl acetate:dichloromethane 1:99, to give methyl 2-[2-(2,2-dimethylpropyl)benzoxazol-5-yl]-2-fluoropropionate (2.06 g).

Workup

  1. customThe cooling bath was removed
  2. temperatureto warm to room temperature
  3. stirringwith stirring over 1½ hours
  4. customThe mixture was quenched with water
  5. extractionextracted with ethyl acetate
  6. extractionThe organic extract
  7. washwas washed with brine
  8. dry with materialdried over anhydrous magnesium sulfate
  9. filtrationfiltered
  10. customthe filtrate was evaporated in vacuo
  11. customThe residue was purified by flash column chromatography on silica gel
  12. washeluting with ethyl acetate:dichloromethane 1:99

Sources & evidence

ORD record
ord-bbb611b505664111a41ca9d6e41c320b
Source dataset
uspto-grants-2004_03
Patent number
US06703347B2

Reaction notes

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