Allyltributylstannane → HCID 21257564, compound

HRID 636291Notes

Reaction equation

HRID 636291 reaction equation
[Li+].[Cl-].[CH2:3]([C:10]1[CH:11]=[C:12]([O:24][CH3:25])[CH:13]=[CH:14][C:15]=1OS(C(F)(F)F)(=O)=O)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[CH2:26]([Sn](CCCC)(CCCC)CCCC)[CH:27]=[CH2:28]>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.CN(C=O)C>[CH2:28]([C:15]1[CH:14]=[CH:13][C:12]([O:24][CH3:25])=[CH:11][C:10]=1[CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)[CH:27]=[CH2:26]

Participants

6

Reactant 3

HCID 90628AllyltributylstannaneHCID 433294Lithium ChlorideHCID 21257572HCID 21257572, compound

Product 1

HCID 21257564HCID 21257564, compoundYield 98.4%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Procedure

LiCl (3.08 g, 72.8 mmol) in a roundbottom flask was flame-dried in high vacuum, and the system was allowed to cool to RT under argon. 3-Benzyl-4-(trifluoromethanesulfonyloxy)anisole (21.0 g, 60.6 mmol), bis(triphenylphosphine)palladium(II) chloride (2.13 g, 3.0 mmol), anhydrous DMF (150 mL), and allyltributyltin (22.6 mL, 72.8 mmol) were added, and the mixture was purged with argon through three evacuation/argon flush cycles. The mixture was heated in an oil bath preset at 95° C., affording a yellow, homogeneous solution. After 1.5 h, the dark mixture was concentrated on the rotavap (high vacuum), and the residue was reconcentrated from xylenes. The resulting residue was taken up in Et2O (120 mL) and stirred briskly with 10% KF (120 mL) for 0.5 h. The layers were separated, and the aqueous layer was extracted with Et2O (2×120 mL). The combined organics were filtered through celite(® to remove the insoluble solids, and the filtrate was washed sequentially with H2O (60 mL) and brine (60 mL). Drying (MgSO4) and concentration left a cloudy, yellow oil. Chromatography (silica gel, 5% EtOAc/hexanes) gave the title compound as a light yellow oil (14.21 g, 98%): TLC Rf (5% EtOAc/hexanes) 0.51; 1H NMR (250 MHz, CDCl3) δ 7.03-7.31 (m, 6H), 6.74 (dd, J=8.3, 2.7 Hz, 1H), 6.66 (d, J=2.7 Hz, 1H), 5.79-5.98 (m, 1H), 4.89-5.07 (m, 2H), 3.97 (s, 2H), 3.75 (s, 3H), 3.21-3.33 (m, 2H); FTIR (CCl4) 1610, 1496, 1256, 1046, 914 cm−1; MS (ES) m/e 239.2 (M+H)+.

Workup

  1. customthe mixture was purged with argon through three evacuation/argon
  2. customflush cycles
  3. temperatureThe mixture was heated in an oil bath preset at 95° C.
  4. customaffording a yellow, homogeneous solution
  5. concentrationthe dark mixture was concentrated on the rotavap (high vacuum)
  6. customThe layers were separated
  7. extractionthe aqueous layer was extracted with Et2O (2×120 mL)
  8. filtrationThe combined organics were filtered through celite(®
  9. customto remove the insoluble solids
  10. washthe filtrate was washed sequentially with H2O (60 mL) and brine (60 mL)
  11. customDrying
  12. concentration(MgSO4) and concentration
  13. waitleft a cloudy, yellow oil

Sources & evidence

ORD record
ord-b25b7baa4c7041dea63b3b6f5d8f5a5a
Source dataset
uspto-grants-2001_02
Patent number
US06191304B1

Reaction notes

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