Triethylamine → 2-Methyl-2-vinyl-1-tetralone

HRID 984739Notes

Reaction equation

HRID 984739 reaction equation
C(N([CH2:6][CH3:7])CC)C.C(Br)=C.[CH3:11][CH:12]1[CH2:21][CH2:20][C:19]2[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=2)[C:13]1=[O:22].CC(C)([O-])C.[Na+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2CCCCC2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2N(C)C)CCCCC1.C1(C)C=CC=CC=1>[CH3:11][C:12]1([CH:6]=[CH2:7])[CH2:21][CH2:20][C:19]2[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=2)[C:13]1=[O:22]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 11641BromoetheneHCID 1026502-Methyl-1-tetraloneHCID 23676156Sodium t-butoxide

Product 1

HCID 113328952-Methyl-2-vinyl-1-tetraloneYield 891.3%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 11375328(+)-2-(Dicyclohexylphosphino)-2'-(dimethylamino)-1,1'-binaphthylCatalystHCID 1140TolueneSolvent

Procedure

An oven dried Schlenk tube equipped with a rubber septum was purged with argon. The septum was removed, and the tube was charged with palladium acetate (5.6 mg, 0.025 mmol, 5 mol %) and (−)-2-(dicyclohexylphosphino)-2′-(dimethylamino)-1,1′-binaphthyl (13.6 mg, 0.028 mmol 5.5 mol %). The tube was capped with the septum, purged with argon, and toluene (2 mL) and triethylamine (5 mg, 0.05 mmol) were added through the septum. The mixture was stirred at room temperature for 3 min, then vinyl bromide (1.0 mL 1.0 mmol) and 2-methyl-1-tetralone (81 mg, 0.5 mmol) were added through the septum. The septum was removed and sodium t-butoxide (96 mg, 1.0 mmol) was added. The tube was capped with the septum and purged with argon. Additional toluene (4 mL) was added and the mixture was stirred at room temperature for 2 h. The mixture was quenched with saturated aqueous ammonium chloride (5 mL), diluted with ether (20 mL), and poured into a separatory funnel. The layers were separated and the aqueous layer was extracted with ether (20 mL). The combined organic layers were washed with brine (20 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The crude material was purified by flash chromatography on silica gel to afford 83 mg (88%) of title compound. The ee was 9 determined to be 79% by chiral HPLC analysis.

Workup

  1. customAn oven dried Schlenk tube
  2. customequipped with a rubber septum
  3. customwas purged with argon
  4. customThe septum was removed
  5. customThe tube was capped with the septum
  6. additionwere added through the septum
  7. customThe septum was removed
  8. customThe tube was capped with the septum
  9. custompurged with argon
  10. additionAdditional toluene (4 mL) was added
  11. stirringthe mixture was stirred at room temperature for 2 h
  12. customThe mixture was quenched with saturated aqueous ammonium chloride (5 mL)
  13. additiondiluted with ether (20 mL)
  14. additionpoured into a separatory funnel
  15. customThe layers were separated
  16. extractionthe aqueous layer was extracted with ether (20 mL)
  17. washThe combined organic layers were washed with brine (20 mL)
  18. dry with materialdried over anhydrous magnesium sulfate
  19. filtrationfiltered
  20. concentrationconcentrated in vacuo
  21. customThe crude material was purified by flash chromatography on silica gel

Sources & evidence

ORD record
ord-bf899a9fdf50424da70d19f94c4a94d2
Source dataset
uspto-grants-2005_03
Patent number
US06867310B1

Reaction notes

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