Triphenylphosphine → 1-Ethyl-1-[2-(trifluoromethyl)-2-propen-1-yl]-1,2,3,4-tetrahydronaphthalene

HRID 600746Notes

Reaction equation

HRID 600746 reaction equation
[CH2:1]([C:3](=[CH2:14])[CH2:4][CH2:5][CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1I)[CH3:2].[F:15][C:16]([F:34])([F:33])[C:17](O)(CC1(C)C2C(=CC=CC=2)CCC1)[CH:18]=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[Cu]I>[CH2:1]([C:3]1([CH2:14][C:17]([C:16]([F:34])([F:33])[F:15])=[CH2:18])[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[CH2:6][CH2:5][CH2:4]1)[CH3:2]

Participants

7

Reactant 3

HCID 11776TriphenylphosphineHCID 116379981-(4-Ethyl-4-penten-1-yl)-2-iodobenzene2×HCID 247491553,3,3-Trifluoro-2-hydroxy-2-[(1-methyl-1,2,3,4-tetrahydro-1-naphthalenyl)methyl]propanal2×

Product 1

HCID 116014351-Ethyl-1-[2-(trifluoromethyl)-2-propen-1-yl]-1,2,3,4-tetrahydronaphthaleneYield 139.2%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Procedure

1-(4-Ethyl-4-penten-1-yl)-2-iodobenzene (Intermediate 11) (1.1 g, 3.66 mmole), tributyl[1-(trifluoromethyl)ethenyl]stannane (Intermediate 3) (1.4 g, 3.64 mmole), triphenyl phosphine (188 mg, 0.717 mmole), palladium acetate (82 mg, 0.365 mmole) and copper(I) iodide (69 mg, 0.362 mmole) were dissolved in dry DMF (60 ml). The solution was degassed by evacuating and filling the flask with nitrogen four times. The solution was then immediately immersed in a 110° C. oil bath, left to react for 3.5 h, cooled to room temperature then partitioned between water (100 ml) and cyclohexane (100 ml). The layers were separated and the aqueous layer was extracted with further cyclohexane (100 ml). The combined extracts were dried over anhydrous sodium sulphate and evaporated and the residue was applied to a silica Solid Phase Extraction (SPE) cartridge. Elution with cyclohexane gave the title compound (1.36 g) containing some residual impurities. This was used without additional purification.

Workup

  1. customThe solution was degassed
  2. customby evacuating
  3. customwas then immediately immersed in a 110° C.
  4. waitleft
  5. customto react for 3.5 h
  6. customthen partitioned between water (100 ml) and cyclohexane (100 ml)
  7. customThe layers were separated
  8. extractionthe aqueous layer was extracted with further cyclohexane (100 ml)
  9. dry with materialThe combined extracts were dried over anhydrous sodium sulphate
  10. customevaporated
  11. extractionthe residue was applied to a silica Solid Phase Extraction (SPE) cartridge
  12. washElution with cyclohexane

Sources & evidence

ORD record
ord-4b383e41778c4b7ab8abb4a9ef0a7cf7
Source dataset
uspto-grants-2011_03
Patent number
US07902224B2

Reaction notes

Loading…