Pyridine → Tert-butyl 4-cyano-3,3-dimethylbutanoate

HRID 1243537Notes

Reaction equation

HRID 1243537 reaction equation
[NH2:1][C:2](=O)[CH2:3][C:4]([CH3:14])([CH3:13])[CH2:5][C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7].N1C=CC=CC=1.FC(F)(F)C(OC(=O)C(F)(F)F)=O.C(OCC)(=O)C>O1CCOCC1>[C:2]([CH2:3][C:4]([CH3:14])([CH3:13])[CH2:5][C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])#[N:1]

Participants

6

Reactant 4

HCID 1049PyridineHCID 8857Ethyl AcetateHCID 9845Trifluoroacetic anhydrideHCID 21927924Tert-butyl 5-amino-3,3-dimethyl-5-oxopentanoate

Product 1

HCID 21927900Tert-butyl 4-cyano-3,3-dimethylbutanoateYield 72.4%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
0 °C

Procedure

Tert-butyl 5-amino-3,3-dimethyl-5-oxopentanoate (3.17 g, 14.7 mmol) was dissolved in dioxane (32 mL) containing pyridine (8 mL) and the solution was cooled to 0° C. Trifluoroacetic anhydride was added dropwise over 25 minutes keeping the temperature between 0–5° C. The mixture was stirred at 0° C. for one hour and then at room temperature overnight. A few chips of ice were added, followed by ethyl acetate (250 mL). The ethyl acetate was washed with brine, dried (Na2SO4) and removed under reduced pressure. The residue was purified by flash chromatography 7:3 (hexane:ethyl acetate) to give 2.1 g (72%) of the desired product. 1H NMR (CDCl3) 2.44 (s, 2H), 2.21 (s, 2H), 1.39 (s, 9H), 1.10 (s, 6H).

Workup

  1. custombetween 0–5° C
  2. customat room temperature
  3. customovernight
  4. additionA few chips of ice were added
  5. washThe ethyl acetate was washed with brine
  6. dry with materialdried (Na2SO4)
  7. customremoved under reduced pressure
  8. customThe residue was purified by flash chromatography 7:3 (hexane:ethyl acetate)

Sources & evidence

ORD record
ord-16986769068c4ed5abe69363c5da97f0
Source dataset
uspto-grants-2006_10
Patent number
US07119098B2

Reaction notes

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