Triphenylphosphine → Tert-butyl 4-[bromo(fluoro)methylidene]piperidine-1-carboxylate

HRID 1895971Notes

Reaction equation

HRID 1895971 reaction equation
O=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Br:34][C:35](Br)(Br)[F:36].C([Zn]CC)C>C1COCC1>[Br:34][C:35]([F:36])=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 67707TribromofluoromethaneHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylateHCID 178418750HCID 178418750, compound

Product 1

HCID 68795703Tert-butyl 4-[bromo(fluoro)methylidene]piperidine-1-carboxylateYield 44%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of tert-butyl 4-oxopiperidine-1-carboxylate (500 mg, 2.52 mmol), triphenylphosphine (808 mg, 3.02 mmol) and tribromofluoromethane (818 mg, 3.02 mmol) in 50 mL of anhydrous THF was added dropwise a solution of diethylzinc (1 M in hexane, 3.02 mL, 3.02 mmol) stirring at r.t. After 2.5 h, the reaction mixture was quenched with MeOH (10 mL), stirred for 30 min., evaporated to dryness in vacuo. Purification was carried out by automated flash liquid chromatography (Horizon™-Biotage) eluting with Petroleum Ether-EtOAc gradient from 95:5:0 to 90:10 to afford the title compound (326 mg).

Workup

  1. customthe reaction mixture was quenched with MeOH (10 mL)
  2. stirringstirred for 30 min.
  3. customevaporated to dryness in vacuo
  4. customPurification
  5. washeluting with Petroleum Ether-EtOAc gradient from 95:5:0 to 90:10

Sources & evidence

ORD record
ord-8a20775d1b9a4a04acddf43d695a702e
Source dataset
uspto-grants-2013_08
Patent number
US08518916B2

Reaction notes

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