Dimethyl malonate → Dimethyl [4-(tert-butoxycarbonyl)phenyl]malonate

HRID 1013510Notes

Reaction equation

HRID 1013510 reaction equation
[C:1]([O:8][CH3:9])(=[O:7])[CH2:2][C:3]([O:5][CH3:6])=[O:4].[O-]P([O-])([O-])=O.[K+].[K+].[K+].[C:18]([O:22][C:23](=[O:31])[C:24]1[CH:29]=[CH:28][C:27](Br)=[CH:26][CH:25]=1)([CH3:21])([CH3:20])[CH3:19]>CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C.C1(C)C=CC=CC=1>[C:18]([O:22][C:23]([C:24]1[CH:29]=[CH:28][C:27]([CH:2]([C:1]([O:8][CH3:9])=[O:7])[C:3]([O:5][CH3:6])=[O:4])=[CH:26][CH:25]=1)=[O:31])([CH3:21])([CH3:19])[CH3:20]

Participants

6

Reactant 3

HCID 7943Dimethyl malonateHCID 62657Potassium Phosphate, TribasicHCID 11334366Tert-butyl 4-bromobenzoate

Product 1

HCID 57541233Dimethyl [4-(tert-butoxycarbonyl)phenyl]malonate

Reagents, catalysts & solvents 2

HCID 178418851HCID 178418851, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

Dimethyl malonate (4.24 g, 32.1 mmol), K3PO4 (18.57 g, 88.0 mmol), and tert-butyl-4-bromobenzoate (7.50 g, 29.2 mmol) were placed in a dry 500 mL flask under N2. Bis(tri-t-butylphosphine)palladium(0) (745 mg, 1.46 mmol) and toluene (100 mL) were added, and the slurry was degassed with N2 for 20 minutes. The reaction was subsequently stirred at 80° C. overnight. The slurry was cooled, diluted with water, and extracted with EtOAc (2×). The combined organic layers were washed with brine, dried (MgSO4), and evaporated. Flash chromatography (0-25% EtOAc/hexanes) afforded dimethyl [4-(tert-butoxycarbonyl)phenyl]malonate as a colorless solid. 1H NMR (CDCl3, 600 MHz) δ 7.96 (d, J=8.5 Hz, 2H), 7.43 (d, J=8.4 Hz, 2H), 4.68 (s, 1H), 3.73 (s, 6H), 1.56 (s, 9H). MS: cal'd 331 (MNa+), exp 331 (MNa+).

Workup

  1. customthe slurry was degassed with N2 for 20 minutes
  2. temperatureThe slurry was cooled
  3. additiondiluted with water
  4. extractionextracted with EtOAc (2×)
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried (MgSO4)
  7. customevaporated

Sources & evidence

ORD record
ord-73d1aaea8b544fdaa2c171c95200dbe3
Source dataset
uspto-grants-2011_07
Patent number
US07981874B2

Reaction notes

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