Potassium Carbonate → tert-Butyl 3-ethynylazetidine-1-carboxylate

HRID 1253505Notes

Reaction equation

HRID 1253505 reaction equation
[CH:1]([CH:3]1[CH2:6][N:5]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH2:4]1)=O.[C:14](=O)([O-])[O-].[K+].[K+].CC(C)C(=O)C(P(=O)([O-])[O-])=[N+]=[N-]>CO>[C:1]([CH:3]1[CH2:6][N:5]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH2:4]1)#[CH:14]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 10726182Tert-butyl 3-formylazetidine-1-carboxylateHCID 86586111Dimethyl-1-diazo-2-oxopropylphosphonate

Product 1

HCID 54349237tert-Butyl 3-ethynylazetidine-1-carboxylate

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

To a solution of tert-butyl 3-formylazetidine-1-carboxylate (96 g, 0.46 mol) and potassium carbonate (128 g, 0.924 mol) in methanol was added dropwise dimethyl-1-diazo-2-oxopropylphosphonate (67 g, 0.35 mol) in 1.6 L of methanol. The mixture was stirred for 2 h and filtered. The filtrate was concentrated and the residue was diluted with 800 ml of methyl-tert-butyl ether and 1 L of 5% w/w aqueous sodium bicarbonate. The layers were separated and the aqueous layer was washed with methyl-tert-butyl ether (2×500 ml). The combined organic layers were dried over magnesium sulfate, filtered and concentrated. The residue was purified by flash column chromatography to afford tert-butyl 3-ethynylazetidine-1-carboxylate.

Workup

  1. filtrationfiltered
  2. concentrationThe filtrate was concentrated
  3. additionthe residue was diluted with 800 ml of methyl-tert-butyl ether and 1 L of 5% w/w aqueous sodium bicarbonate
  4. customThe layers were separated
  5. washthe aqueous layer was washed with methyl-tert-butyl ether (2×500 ml)
  6. dry with materialThe combined organic layers were dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by flash column chromatography

Sources & evidence

ORD record
ord-dfb4335b6e2e4d2497d86542d92c645d
Source dataset
uspto-grants-2013_06
Patent number
US08455477B2

Reaction notes

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