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

HRID 1506163Notes

Reaction equation

HRID 1506163 reaction equation
CC(C)([O-])C.[K+].[C:7]([CH2:9]P(=O)(OCC)OCC)#[N:8].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:7]([CH:9]=[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:8]

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

Potassium tert-butoxide (2.03 g, 21.1 mmol) in tetrahydrofuran (20 mL) was mixed with diethyl cyanomethylphosphonate (3.54 g, 20.0 mmol) in tetrahydrofuran (20 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) obtained in Reference Synthetic Examplea 112 in-tetrahydrofuran (20 mL) under cooling with ice and then stirred at room temperature for 1 day. After addition of water, the reaction mixture was extracted with ethyl acetate. The organic layer was washed with saturated sodium chloride, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The 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. temperatureunder cooling with ice
  3. stirringstirred at room temperature for 1 day
  4. extractionthe reaction mixture was extracted with ethyl acetate
  5. washThe organic layer was washed with saturated sodium chloride
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=3/1 (v/v))

Sources & evidence

ORD record
ord-aa74921b22af4237847c9030482f1e10
Source dataset
uspto-grants-2015_12
Patent number
US09216999B2

Reaction notes

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