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

HRID 2406236Notes

Reaction equation

HRID 2406236 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 83.7%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

4-Trimethylsilanyloxy-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester (0.60 g, 2.2 mmol) was dissolved in MeCN and Selectfluor (0.86 g, 2.4 mmol) is added. The reaction was stirred at ambient temperature for 75 minutes, and then poured into EtOAc (100 mL). The organics were washed with dilute brine and saturated brine, then dried (Na2SO4), filtered and concentrated. Purification by flash chromatography on silica gel (0-50% EtOAc/Hept) afforded 3-fluoro-4-oxo-piperidine-1-carboxylic acid tert-butyl ester (0.40 g, 83% yield). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 4.64-4.91 (m, 1H), 4.39 (d, 1H), 4.11 (td, J=6.57, 3.03 Hz, 1H), 3.10-3.24 (m, 2H), 2.40-2.61 (m, 2H), 1.43 (s, 9H).

Workup

  1. washThe organics were washed with dilute brine and saturated brine
  2. dry with materialdried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customPurification by flash chromatography on silica gel (0-50% EtOAc/Hept)

Sources & evidence

ORD record
ord-cd771df2f29f4c00834b7ad0bcfbec03
Source dataset
uspto-grants-2014_08
Patent number
US08809352B2

Reaction notes

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