Dimethylformamide → HCID 117667669, compound

HRID 514206Notes

Reaction equation

HRID 514206 reaction equation
Br[C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([C:9]2[C:10](=[O:21])[CH:11]3[CH:16]([C:17]=2[O:18]C)[CH:15]2[O:20][CH:12]3[CH2:13][CH2:14]2)=[C:4]([CH3:22])[CH:3]=1.[F-].[Cs+].CN(C)C=O.[CH2:30]([Sn](CCCC)(CCCC)C#CC)[CH2:31][CH2:32]C>O.C(OCC)(=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:8][C:6]1[CH:7]=[C:2]([C:30]#[C:31][CH3:32])[CH:3]=[C:4]([CH3:22])[C:5]=1[CH:9]1[C:10](=[O:21])[CH:11]2[CH:16]([CH:15]3[O:20][CH:12]2[CH2:13][CH2:14]3)[C:17]1=[O:18]

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 25953Cesium fluorideHCID 2733165Tributyl(prop-1-yn-1-yl)stannaneHCID 117667862HCID 117667862, compound

Product 1

HCID 117667669HCID 117667669, compound

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

To (1RS,2SR,6RS,7SR)-4-(4-bromo-2,6-dimethylphenyl)-5-methoxy-10-oxa-tricyclo[5.2.1.02,6]dec-4-en-3-one (0.40 g, 1.10 mmol), cesium fluoride (0.34 g, 2.20 mmol), cuprous iodide (0.04 g, 0.22 mmol) and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.12 g, 0.17 mmol) under nitrogen atmosphere is added anhydrous dimethylformamide (3.8 g, 4 ml, 51 mmol) followed by tributyl(prop-1-ynyl)stannane (1.10 g, 1.0 ml, 3.3 mmol). The mixture is heated at 120°C. under microwave irradiation for 60 minutes then diluted with water (50 ml) and ethyl acetate (50 ml) and filtered through a bed of diatomaceous earth. The residue is washed with ethyl acetate and the crude product is extracted with ethyl acetate (50 ml×2). The combined organic fractions are washed with distilled water then brine, dried over magnesium sulfate, filtered and concentrated in vacuo. The crude product is purified by flash column chromatography to afford (1RS,2SR,6RS,7SR)-4-(2,6-dimethyl-4-prop-1-ynylphenyl)-10-oxatricyclo[5.2.1.02,6]decane-3,5-dione.

Workup

  1. filtrationfiltered through a bed of diatomaceous earth
  2. washThe residue is washed with ethyl acetate
  3. extractionthe crude product is extracted with ethyl acetate (50 ml×2)
  4. washThe combined organic fractions are washed with distilled water
  5. dry with materialbrine, dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe crude product is purified by flash column chromatography

Sources & evidence

ORD record
ord-ffde3d1564a645859faed47382fef056
Source dataset
uspto-grants-2015_08
Patent number
US09107415B2

Reaction notes

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