Potassium Carbonate → (S)-tert-butyl 2-(4-ethynylphenyl)morpholine-4-carboxylate

HRID 710243Notes

Reaction equation

HRID 710243 reaction equation
[CH:1]([C:3]1[CH:8]=[CH:7][C:6]([C@@H:9]2[O:14][CH2:13][CH2:12][N:11]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:10]2)=[CH:5][CH:4]=1)=O.[C:22](=O)([O-])[O-].[K+].[K+].[N+](=C(P(=O)(OC)OC)C(=O)C)=[N-].C(=O)(O)[O-].[Na+]>CO.C(OCC)(=O)C>[C:1]([C:3]1[CH:8]=[CH:7][C:6]([C@@H:9]2[O:14][CH2:13][CH2:12][N:11]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:10]2)=[CH:5][CH:4]=1)#[CH:22]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 516892Sodium BicarbonateHCID 86654636(S)-tert-Butyl 2-(4-formylphenyl)morpholine-4-carboxylateHCID 136023029(1E)-1-diazo-1-dimethoxyphosphorylpropan-2-one

Product 1

HCID 89689402(S)-tert-butyl 2-(4-ethynylphenyl)morpholine-4-carboxylateYield 87.4%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

(S)-tert-Butyl 2-(4-formylphenyl)morpholine-4-carboxylate (120 mg, 0.41 mmol) was dissolved in methanol (5 ml), then potassium carbonate (114 mg, 0.824 mmol) was added, followed by dimethyl 1-diazo-2-oxopropylphosphonate (99 mg, 0.515 mmol). The mixture was stirred for 2 h at room temperature. Ethyl acetate (50 ml) and sodium bicarbonate solution (50 ml) were added, the aqueous phase re-extracted with ethyl acetate. The combined organic layers were dried (MgSO4) and evaporated. The residue was purified by flash chromatography (10 g silica gel, 10 to 20% ethyl acetate in heptane) to yield a colorless oil (103 mg, 87%).

Workup

  1. extractionthe aqueous phase re-extracted with ethyl acetate
  2. dry with materialThe combined organic layers were dried (MgSO4)
  3. customevaporated
  4. customThe residue was purified by flash chromatography (10 g silica gel, 10 to 20% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-8f7d5a62be6545b2b1842141e3d47d63
Source dataset
uspto-grants-2015_11
Patent number
US09181230B2

Reaction notes

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