Trimethylsilylacetylene → 6-Ethynyl-7-methoxy-1,1-dimethyl-3,4-dihydro-1H-naphthalen-2-one

HRID 2275268Notes

Reaction equation

HRID 2275268 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1[O:12][CH3:13])[C:8]([CH3:15])([CH3:14])[C:7](=[O:16])[CH2:6][CH2:5]2.[CH3:17][CH:18](C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C.C[Si](C#C)(C)C>C(#N)C.C(OCC)(=O)C>[C:17]([C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1[O:12][CH3:13])[C:8]([CH3:15])([CH3:14])[C:7](=[O:16])[CH2:6][CH2:5]2)#[CH:18]

Participants

6

Reactant 3

HCID 66111TrimethylsilylacetyleneHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 545785436-Bromo-7-methoxy-1,1-dimethyl-3,4-dihydronaphthalen-2(1H)-one

Product 1

HCID 866638296-Ethynyl-7-methoxy-1,1-dimethyl-3,4-dihydro-1H-naphthalen-2-oneYield 430.1%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
85 °C

Procedure

6-Bromo-7-methoxy-1,1-dimethyl-3,4-dihydro-1H-naphthalen-2-one (1 g) was dissolved in acetonitrile (50 ml), added with PdCl2(CH3CN)2 (45 mg), X-phos (168 mg), CsCO3 (1.2 g) and trimethylsilylacetylene (0.9 ml), and the mixture was stirred at 85° C. for 2 hrs. The reaction mixture was diluted with ethyl acetate (100 ml). The organic layer was washed twice with 10% brine and concentrated under reduced pressure. The resulting residues were dissolved in THF (10 ml), added with the THF solution (4 ml) comprising tetrabutylammonium fluoride and stirred at room temperature for 1 hr. The reaction mixture was diluted with ethyl acetate (100 ml). The organic layer was washed twice with 10% brine and concentrated under reduced pressure. The resulting residues were purified by silica gel column (n-hexane/ethyl acetate=9/1) to obtain the title compound (346 mg, two step yield 43%).

Workup

  1. washThe organic layer was washed twice with 10% brine
  2. concentrationconcentrated under reduced pressure
  3. dissolutionThe resulting residues were dissolved in THF (10 ml)
  4. additionadded with the THF solution (4 ml)
  5. stirringstirred at room temperature for 1 hr
  6. additionThe reaction mixture was diluted with ethyl acetate (100 ml)
  7. washThe organic layer was washed twice with 10% brine
  8. concentrationconcentrated under reduced pressure
  9. customThe resulting residues were purified by silica gel column (n-hexane/ethyl acetate=9/1)

Sources & evidence

ORD record
ord-3efccaaa131846bd910a189d9ebb834d
Source dataset
uspto-grants-2015_09
Patent number
US09126931B2

Reaction notes

Loading…