Lithium Chloride → methyl (2E)-3-[4-(9a-butyl-7-methoxy-3-oxo-2,3,9,9a-tetrahydro-1H-fluoren-4-yl)phenyl]-2-propenoate

HRID 7843

Reaction equation

HRID 7843 reaction equation
[CH2:1]([C:5]12[CH2:17][CH2:16][C:15](=[O:18])[C:14]([C:19]3[CH:24]=[CH:23][C:22](OS(C(F)(F)F)(=O)=O)=[CH:21][CH:20]=3)=[C:13]1[C:12]1[C:7](=[CH:8][C:9]([O:33][CH3:34])=[CH:10][CH:11]=1)[CH2:6]2)[CH2:2][CH2:3][CH3:4].C([Sn](CCCC)(CCCC)/[CH:40]=[CH:41]/[C:42]([O:44][CH3:45])=[O:43])CCC.[Cl-].[Li+]>CN(C)C=O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH2:1]([C:5]12[CH2:17][CH2:16][C:15](=[O:18])[C:14]([C:19]3[CH:20]=[CH:21][C:22](/[CH:40]=[CH:41]/[C:42]([O:44][CH3:45])=[O:43])=[CH:23][CH:24]=3)=[C:13]1[C:12]1[C:7](=[CH:8][C:9]([O:33][CH3:34])=[CH:10][CH:11]=1)[CH2:6]2)[CH2:2][CH2:3][CH3:4]

Participants

6

Reactant 3

HCID 433294Lithium ChlorideHCID 11824926Methyl 3-(tributylstannyl)prop-2-enoateHCID 219909189a-butyl-7-methoxy-4-[4-(trifluoromethane-sulfonyloxy)-phenyl]-1,2,9,9a-tetrahydro-3H-fluoren-3-one

Product 1

HCID 67400795methyl (2E)-3-[4-(9a-butyl-7-methoxy-3-oxo-2,3,9,9a-tetrahydro-1H-fluoren-4-yl)phenyl]-2-propenoateYield 96.4%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of 9a-butyl-7-methoxy-4-[4-(trifluoromethane-sulfonyloxy)-phenyl]-1,2,9,9a-tetrahydro-3H-fluoren-3-one (98.9 mg, 0.2 mmol), methyl (E)-3-tributylstannyl-acrylate (112.5 mg, 0.3 mmol) and lithium chloride (25.4 mg, 0.6 mmol) in anhydrous dimethylformamide (1.0 mL) was purged with nitrogen and treated with bis(triphenylphosphine)palladium(II) chloride (7.0 mg, 0.01 mmol). The resulting mixture was purged with nitrogen then stirred under a nitrogen atmosphere with heating in an oil bath at 90° C. for 60 minutes. After cooling, the solvent was evaporated under vacuum. The residue in EtOAc (10 mL) was washed with water (2×5 mL) and brine (5 ml), dried over MgSO4, filtered, and evaporated under vacuum to a gum (194 mg). The crude product was purified by preparative layer chromatography (PLC) on two 0.1×20×20 cm silica gel GF plates, developing with 4:1-hexanes-EtOAc. The major UV visible band at Rf 0.15-0.25 was eluted with EtOAc and the solvent evaporated under vacuum to afford methyl (2E)-3-[4-(9a-butyl-7-methoxy-3-oxo-2,3,9,9a-tetrahydro-1H-fluoren-4-yl)phenyl]-2-propenoate (83 mg) as a pale yellow solid. NMR showed approximately 7-8% of a Bu3SnX impurity.

Workup

  1. customwas purged with nitrogen
  2. customThe resulting mixture was purged with nitrogen
  3. temperatureAfter cooling
  4. customthe solvent was evaporated under vacuum
  5. washThe residue in EtOAc (10 mL) was washed with water (2×5 mL) and brine (5 ml)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. customevaporated under vacuum to a gum (194 mg)
  9. customThe crude product was purified by preparative layer chromatography (PLC) on two 0.1×20×20 cm silica gel GF plates
  10. washThe major UV visible band at Rf 0.15-0.25 was eluted with EtOAc
  11. customthe solvent evaporated under vacuum

Sources & evidence

ORD record
ord-adef68c798704d7e9c50dde96c01cffe
Source dataset
uspto-grants-2006_08
Patent number
US07087599B2

Linked notes

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