Water → 1-(tert-Butoxycarbonyl)-3-(cyanomethylene)azetidine

HRID 1506254Notes

Reaction equation

HRID 1506254 reaction equation
[C:1]([CH2:3]P(=O)(OCC)OCC)#[N:2].CC(C)([O-])C.[K+].O=[C:19]1[CH2:22][N:21]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])[CH2:20]1.O>O1CCCC1>[C:1]([CH:3]=[C:19]1[CH2:22][N:21]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])[CH2:20]1)#[N:2]

Participants

6

Reactant 4

HCID 962WaterHCID 75676Diethyl (cyanomethyl)phosphonateHCID 15194043-Oxo-azetidine-1-carboxylic acid tert-butyl esterHCID 23665647Potassium tert-butoxide

Product 1

HCID 457892161-(tert-Butoxycarbonyl)-3-(cyanomethylene)azetidineYield 58%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

Diethyl cyanomethylphosphonate (3.54 g, 20.0 mmom) in tetrahydrofuran (20 mL) was added to potassium tert-butoxide (2.03 g, 21.1 mmol) in tetrahydrofuran (30 mL) under cooling with ice and stirred for 30 minutes. The reaction mixture was mixed with tert-butyl 3-oxoazetidine-1-carboxylate (2.96 g, 17.3 mmol) in tetrahydrofuran (15 mL) and stirred at room temperature for 1 day, and after addition of water, extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/ethyl acetate=3/1 (v/v)) to give the title compound as a colorless solid (1.93 g, yield 58%).

Workup

  1. temperatureunder cooling with ice
  2. stirringstirred at room temperature for 1 day
  3. extractionextracted with ethyl acetate
  4. washThe organic layer was washed with saturated aqueous sodium chloride
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe resulting residue was purified by silica gel column chromatography (hexane/ethyl acetate=3/1 (v/v))

Sources & evidence

ORD record
ord-e1e27029cad842c1b78600b463b46ea1
Source dataset
uspto-grants-2015_12
Patent number
US09216999B2

Reaction notes

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