Selectfluor → TERT-BUTYL 3-FLUORO-4-OXOPIPERIDINE-1-CARBOXYLATE

HRID 2043527Notes

Reaction equation

HRID 2043527 reaction equation
C[Si](C)(C)[O:3][C:4]1[CH2:9][CH2:8][N:7]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:6][CH:5]=1.[B-](F)(F)(F)[F:20].[B-](F)(F)(F)F.C1[N+]2(CCl)CC[N+](F)(CC2)C1>C(#N)C.C(OCC)(=O)C>[F:20][CH:9]1[C:4](=[O:3])[CH2:5][CH2:6][N:7]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:8]1

Participants

5

Reactant 2

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

Product 1

HCID 10560711TERT-BUTYL 3-FLUORO-4-OXOPIPERIDINE-1-CARBOXYLATEYield 88%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of compound 129 (4.5 g, 16.578 mmol) in dry acetonitrile (175 mL) was treated with Selectfluor™ (6.46 g, 18.236 mmol) at room temperature and resulting solution was stirred for 75 min. at same temperature. The reaction was diluted with ethyl acetate (500 mL), washed with unsaturated brine (300 mL, water: saturated brine 1:1), saturated brine (100 mL) and dried (Na2SO4). The solvent was evaporated and crude was purified by column chromatography (ethyl acetate to 5% methanol in ethyl acetate) to obtain compound 130 (3.18 g, 88%) as a syrup. 1H NMR (CDCl3) δ: 1.50 (s, 9H), 2.46-2.64 (m, 2H), 3.20-3.37 (m, 2H), 4.13-4.20 (m, 1H), 4.44-4.48 (m, 1H), 4.72-4.77, 4.88-4.93 (2m, 1H). 1H NMR comparable with literature (J. Med. Chem. 1999, 42, 2087-2104).

Workup

  1. customresulting solution
  2. washwashed with unsaturated brine (300 mL, water: saturated brine 1:1), saturated brine (100 mL)
  3. dry with materialdried (Na2SO4)
  4. customThe solvent was evaporated
  5. customcrude was purified by column chromatography (ethyl acetate to 5% methanol in ethyl acetate)

Sources & evidence

ORD record
ord-276eba39dec4433f848b57a347278774
Source dataset
uspto-grants-2013_11
Patent number
US08586620B2

Reaction notes

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