tert-Butyl acrylate → HCID 59456950, compound

HRID 1362094Notes

Reaction equation

HRID 1362094 reaction equation
Br[C:2]1[CH:3]=[C:4]2[O:10][C:9](=[O:11])[NH:8][C:5]2=[N:6][CH:7]=1.[C:12]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])(=[O:15])[CH:13]=[CH2:14].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(CC)C(C)C)(C)C>CN(C)C=O.C(#N)CC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:17]([O:16][C:12](=[O:15])/[CH:13]=[CH:14]/[C:2]1[CH:3]=[C:4]2[O:10][C:9](=[O:11])[NH:8][C:5]2=[N:6][CH:7]=1)([CH3:20])([CH3:19])[CH3:18]

Participants

8

Reactant 4

HCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 81531DiisopropylethylamineHCID 136144586-Bromo-3H-oxazolo(4,5-b)pyridin-2-one

Product 1

HCID 59456950HCID 59456950, compoundYield 23.2%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 7854PropionitrileSolvent

Procedure

A stirred solution of 6-bromo-3H-oxazolo[4,5-b]pyridin-2-one (1.00 g, 4.65 mmol), tert-butyl acrylate (2.7 mL, 18 mmol), palladium(II) acetate (104 mg, 0.465 mmol), tri-o-tolylphosphine (283 mg, 0.930 mmol), and N,N-diisopropylethylamine (1.7 mL, 9.7 mmol) in N,N-dimethylformamide (4 mL) and propionitrile (16 mL) was deoxygenated by bubbling argon through the solution for 20 min. The mixture was heated to reflux for 21 h, then allowed to cool. The mixture was concentrated in vacuo. The residue was dissolved in dichloromethane (100 mL). The solution was washed with water (2×200 mL), dried over sodium sulfate, filtered, and the solvent removed in vacuo to give a dark brown oil. Purification by flash column chromatography (silica gel, gradient from 98:2 to 94:6 CHCl3/MeOH) gave the title compound (283 mg, 23%) as a brown solid: 1H NMR (300 MHz, CDCl3) δ 8.24 (d, J=1.4 Hz, 1H), 7.64-7.55 (m, 2H), 6.37 (d, J=16.0 Hz, 1H), 1.55 (s, 9H).

Workup

  1. customby bubbling argon through the solution for 20 min
  2. temperatureThe mixture was heated
  3. temperatureto reflux for 21 h
  4. temperatureto cool
  5. concentrationThe mixture was concentrated in vacuo
  6. dissolutionThe residue was dissolved in dichloromethane (100 mL)
  7. washThe solution was washed with water (2×200 mL)
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. customthe solvent removed in vacuo
  11. customto give a dark brown oil
  12. customPurification by flash column chromatography (silica gel, gradient from 98:2 to 94:6 CHCl3/MeOH)

Sources & evidence

ORD record
ord-3ae5b42cbed54f7b8cf9d7fd259020d3
Source dataset
uspto-grants-2011_02
Patent number
US07879872B2

Reaction notes

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