Tributylvinyltin → HCID 67168875, compound

HRID 1506309Notes

Reaction equation

HRID 1506309 reaction equation
FC(F)(F)S(O[C:7]1[CH:16]=[CH:15][C:14]2[C:13](=[O:17])[CH2:12][CH2:11][C:10]([CH3:19])([CH3:18])[C:9]=2[CH:8]=1)(=O)=O.[CH2:22]([Sn](CCCC)(CCCC)C=C)[CH2:23]CC.[Cl-].[Li+]>O1CCOCC1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:18][C:10]1([CH3:19])[C:9]2[C:14](=[CH:15][CH:16]=[C:7]([CH:22]=[CH2:23])[CH:8]=2)[C:13](=[O:17])[CH2:12][CH2:11]1

Participants

6

Reactant 3

HCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 225687874,4-Dimethyl-6-trifluoromethylsulfonyloxy-1,2,3,4-tetrahydronaphthalene-1-one

Product 1

HCID 67168875HCID 67168875, compoundYield 73%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 8,8-dimethyl-5-oxo-5,6,7,8-tetrahydronaphthalen-2-yl trifluoromethanesulfonate (Preparation 1B, 0.443 g, 1.37 mmol) in dioxane (2.5 mL) in a sealed tube was added sequentially tributyl(vinyl)stannane (0.444 mL, 1.51 mmol) and lithium chloride (0.175 g, 4.12 mmol). The mixture was degassed under reduced pressure and charged with nitrogen (2×). To the mixture was added tetrakis(triphenylphosphine) palladium(0) (0.159 g, 0.137 mmol), and the mixture was stirred under a strong stream of nitrogen for 5 min. The reaction mixture was sealed, immersed in an oil bath at 100° C., and stirred at room temperature overnight. The reaction mixture was filtered under reduced pressure, and the solid was rinsed with ethyl acetate (˜50 mL total). The filtrate was concentrated under reduced pressure, and the resulting residue was diluted with ether (˜25 mL). The resulting solid was removed by vacuum filtration and rinsed with ether (˜25 mL). The filtrate was concentrated under reduced pressure and purified by flash silica gel chromatography using a mixture of ethyl acetate in hexane (5%-10%) to give 4,4-dimethyl-6-vinyl-3,4-dihydronaphthalen-1(2H)-one (0.201 g, 1.00 mmol, 73. % yield) as a colorless oil. The product had an HPLC ret. time=2.55 min. (condition A); LC/MS M+1=200.9.

Workup

  1. customThe mixture was degassed under reduced pressure
  2. additioncharged with nitrogen (2×)
  3. customThe reaction mixture was sealed
  4. customimmersed in an oil bath at 100° C.
  5. stirringstirred at room temperature overnight
  6. filtrationThe reaction mixture was filtered under reduced pressure
  7. washthe solid was rinsed with ethyl acetate (˜50 mL total)
  8. concentrationThe filtrate was concentrated under reduced pressure
  9. additionthe resulting residue was diluted with ether (˜25 mL)
  10. customThe resulting solid was removed by vacuum filtration
  11. washrinsed with ether (˜25 mL)
  12. concentrationThe filtrate was concentrated under reduced pressure
  13. custompurified by flash silica gel chromatography
  14. additiona mixture of ethyl acetate in hexane (5%-10%)

Sources & evidence

ORD record
ord-76f8697836ee4118bb85df2c175868f0
Source dataset
uspto-grants-2015_12
Patent number
US09216972B2

Reaction notes

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