Trimethylsilylacetylene → HCID 86754307, compound

HRID 583315Notes

Reaction equation

HRID 583315 reaction equation
[CH3:1][O:2][C:3](=[O:31])[C:4]1[CH:9]=[C:8](Br)[CH:7]=[C:6]([CH3:11])[C:5]=1[N:12]([CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[S:13]([C:16]1[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=1)(=[O:15])=[O:14].C[Si]([C:36]#[CH:37])(C)C>CN(C=O)C.C(N(CC)CC)C.CCOCC.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu]I>[CH3:1][O:2][C:3](=[O:31])[C:4]1[CH:9]=[C:8]([C:36]#[CH:37])[CH:7]=[C:6]([CH3:11])[C:5]=1[N:12]([CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[S:13]([C:16]1[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=1)(=[O:15])=[O:14]

Participants

8

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 70052828HCID 70052828, compound

Product 1

HCID 86754307HCID 86754307, compoundYield 80%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent

Procedure

To a solution of 0.277 g (0.50 mmol) of the product of Example 11 in 2.0 mL of DMF and 2.0 mL of triethylamine was added 0.39 mL (0.2.748 mmol) of trimetylsilyl acetylene, 19 mg (0.027 mmol) of bis(triphenylphosphine)palladium(II)dichloride and 2.6 mg of copper(I)iodide. The reaction mixture was then heated to 65 degrees for 2 h and then cooled to room temperature and diluted with ether. The organics were washed with 5% Hcl solution, water and brine, dried over MgSO4, filtered and concentrated in vacuo. The residue was dissolved in 5 mL of THF, 1 mL of 1M tetrbutylammonium fluoride-THF solution was added and the reaction was stirred at room temperatue for 1 h, then diluted with ether, washed with 5% HCl solution, water and brine, dried over MgSO4, filtered and concentrated in vacuo. The residue was chromatographed on silica eluting with EtOAc-Hex (1:10) to provide 0.197 g (80%) of the desired product as a white foam. Electrospray Mass Spec: 450.3 (M+H)+.

Workup

  1. temperatureThe reaction mixture was then heated to 65 degrees for 2 h
  2. washThe organics were washed with 5% Hcl solution, water and brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. dissolutionThe residue was dissolved in 5 mL of THF
  7. addition1 mL of 1M tetrbutylammonium fluoride-THF solution was added
  8. additiondiluted with ether
  9. washwashed with 5% HCl solution, water and brine
  10. dry with materialdried over MgSO4
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo
  13. customThe residue was chromatographed on silica eluting with EtOAc-Hex (1:10)

Sources & evidence

ORD record
ord-2547104c9e5247c28934493ebcc1f25c
Source dataset
uspto-grants-1999_07
Patent number
US05929097

Reaction notes

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