Ethyl Acetate → TERT-BUTYL 3-FLUORO-4-OXOPIPERIDINE-1-CARBOXYLATE

HRID 350580Notes

Reaction equation

HRID 350580 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH:12]=[C:11]([O:14][Si](C)(C)C)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[B-](F)(F)(F)[F:20].[B-](F)(F)(F)F.C1[N+]2(CCl)CC[N+](F)(CC2)C1.CCOC(C)=O>CC#N>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C:11](=[O:14])[CH:10]([F:20])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 2724933SelectfluorHCID 10778540tert-Butyl 4-((trimethylsilyl)oxy)-5,6-dihydropyridine-1(2H)-carboxylate

Product 1

HCID 10560711TERT-BUTYL 3-FLUORO-4-OXOPIPERIDINE-1-CARBOXYLATEYield 89%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of 1-tert-butoxycarbonyl-1,2,3,6-tetrahydro-4-(trimethylsilyloxy)pyridine (20.4 g, 75.0 mmol) in CH3CN (500 mL) was added Selectfluor™ (29.2 g, 82.5 mmol) at room temperature, and the reaction mixture was stirred for 2 hr. EtOAc was added to the reaction mixture, and the mixture was washed with brine, dried over Na2SO4, and concentrated to dryness. Chromatography of the residue with CHCl3-MeOH (6:1, v/v) as eluent gave 1-tert-butoxycarbonyl-3-fluoro-4-piperidone (14.5 g, 89%) as a colorless oil. 1H-NMR (CDCl3) δ 1.50 (s, 9H), 2.44 (t, J=6.9 Hz, 1H), 2.48–2.63 (m, 2H), 3.26 (ddd, J=13.5, 10.5, 3.9 Hz, 1H), 3.72 (t, J=6.9 Hz, 1H), 4.16 (m, 1H), 4.42 (m, 1H), 4.83 (dt, 49.2, 6.9 Hz, 1H).

Workup

  1. washthe mixture was washed with brine
  2. dry with materialdried over Na2SO4
  3. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-d0438c4e5bb04d13a2030d8dd8aec03d
Source dataset
uspto-grants-2007_02
Patent number
US07179819B2

Reaction notes

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