Cesium carbonate → 1-(5-Tert-butyl-2-methoxy-3-nitro-phenyl)-azetidin-2-one

HRID 1181933Notes

Reaction equation

HRID 1181933 reaction equation
Br[C:2]1[CH:7]=[C:6]([C:8]([CH3:11])([CH3:10])[CH3:9])[CH:5]=[C:4]([N+:12]([O-:14])=[O:13])[C:3]=1[O:15][CH3:16].[NH:17]1[CH2:20][CH2:19][C:18]1=[O:21].C(=O)([O-])[O-].[Cs+].[Cs+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>[C:8]([C:6]1[CH:5]=[C:4]([N+:12]([O-:14])=[O:13])[C:3]([O:15][CH3:16])=[C:2]([N:17]2[CH2:20][CH2:19][C:18]2=[O:21])[CH:7]=1)([CH3:11])([CH3:10])[CH3:9]

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 1367212-AzetidinoneHCID 575500241-Bromo-5-(tert-butyl)-2-methoxy-3-nitrobenzene

Product 1

HCID 575500231-(5-Tert-butyl-2-methoxy-3-nitro-phenyl)-azetidin-2-oneYield 106.6%

Reagents, catalysts & solvents 2

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Conditions

Temperature
100 °C

Procedure

An oven-dried Schlenk tube was charged with the above nitroanisole (500 mg, 1.74 mmol), 2-azetidinone (150 mg, 2.1 mmol), tris(dibenzylideneacetone)dipalladium(0) (32 mg, 0.035 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (58 mg, 0.1 mmol) and cesium carbonate (795 mg, 2.44 mmol). The tube was capped with a rubber septum, purged with argon and 1,4-dioxane (7 mL) was then added through the septum via a syringe. The tube was sealed with a teflon screwcap and the reaction mixture was stirred at 100° C. for 20 h. The reaction mixture was cooled to room temperature, diluted with EtOAc (100 mL), washed with water, brine and dried over anhydrous Na2SO4. The solvent was removed in vacuo, and the crude product was purified by column chromatography (2:1 hexane-EtOAc) to give 1-(5-tert-butyl-2-methoxy-3-nitro-phenyl)-azetidin-2-one (516 mg, quantitative).

Workup

  1. customThe tube was capped with a rubber septum
  2. custompurged with argon and 1,4-dioxane (7 mL)
  3. additionwas then added through the septum via a syringe
  4. customThe tube was sealed with a teflon screwcap
  5. temperatureThe reaction mixture was cooled to room temperature
  6. additiondiluted with EtOAc (100 mL)
  7. washwashed with water, brine
  8. dry with materialdried over anhydrous Na2SO4
  9. customThe solvent was removed in vacuo
  10. customthe crude product was purified by column chromatography (2:1 hexane-EtOAc)

Sources & evidence

ORD record
ord-23afa50e6cbd4b979c2c394a0b72534a
Source dataset
uspto-grants-2007_10
Patent number
US07285545B2

Reaction notes

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