Selectfluor → Benzyl 3-fluoro-4-oxopiperidine-1-carboxylate

HRID 1926646Notes

Reaction equation

HRID 1926646 reaction equation
C[Si](C)(C)[O:3][C:4]1[CH2:5][CH2:6][N:7]([C:10]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[O:11])[CH2:8][CH:9]=1.[B-](F)(F)(F)[F:23].[B-](F)(F)(F)F.C1[N+]2(CCl)CC[N+](F)(CC2)C1>C(#N)C>[F:23][CH:5]1[C:4](=[O:3])[CH2:9][CH2:8][N:7]([C:10]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[O:11])[CH2:6]1

Participants

4

Reactant 2

HCID 2724933SelectfluorHCID 57502431Benzyl 4-((trimethylsilyl)oxy)-5,6-dihydropyridine-1(2H)-carboxylate

Product 1

HCID 42609253Benzyl 3-fluoro-4-oxopiperidine-1-carboxylate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of benzyl 4-[(trimethylsilyl)oxy]-3,6-dihydropyridine-1(2H)-carboxylate (800 g, 2.61 mol) in acetonitrile was added Selectfluor™ (932.8 g, 2.63 mol) in small portions under nitrogen at 0° C. After the addition was complete, the reaction mixture was allowed to warm to room temperature and stirred overnight. TLC (EtOAc/petroleum ether=1:1) indicated the reaction was complete, and the solvent was removed in vacuo. The residue was triturated with ethyl acetate (5 L, 3 L) for 30 min and filtered. The filtrate was concentrated and the syrup was purified by column chromatography (EtOAc/petroleum ether=1:10 to 2:3) to afford benzyl 3-fluoro-4-oxopiperidine-1-carboxylate. 1H NMR (600 MHz, CDCl3-D6) 7.40-7.30 (m, 5H); 5.20 (s, 2H); 5.00-4.70 (d, 1H); 5.20-4.90 (d, 1H); 4.30-4.20 (m, 1H); 3.40-3.20 (m, 2H); 2.50 (s, 2H).

Workup

  1. additionAfter the addition
  2. customthe solvent was removed in vacuo
  3. customThe residue was triturated with ethyl acetate (5 L, 3 L) for 30 min
  4. filtrationfiltered
  5. concentrationThe filtrate was concentrated
  6. customthe syrup was purified by column chromatography (EtOAc/petroleum ether=1:10 to 2:3)

Sources & evidence

ORD record
ord-54252fe33a6e4efb926a06b49a7919a6
Source dataset
uspto-grants-2012_05
Patent number
US08183245B2

Reaction notes

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