Trimethylsilylacetylene → HCID 21957873, compound

HRID 619620Notes

Reaction equation

HRID 619620 reaction equation
FC(F)(F)S(O[C:7]1[CH:8]=[C:9]2[C:14](=[CH:15][CH:16]=1)[S:13][C:12]([CH3:18])([CH3:17])[CH2:11][C:10]2=[O:19])(=O)=O.[CH3:22][Si:23]([C:26]#[CH:27])([CH3:25])[CH3:24]>CCN(CC)CC.CN(C=O)C.O.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>[CH3:17][C:12]1([CH3:18])[CH2:11][C:10](=[O:19])[C:9]2[C:14](=[CH:15][CH:16]=[C:7]([C:27]#[C:26][Si:23]([CH3:25])([CH3:24])[CH3:22])[CH:8]=2)[S:13]1

Participants

7

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 10286711HCID 10286711, compound2×

Product 1

HCID 21957873HCID 21957873, compoundYield 91%

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
95 °C

Procedure

A solution of 2,2-dimethyl-4-oxo-thiochroman-6-yl trifluoromethanesulfonate (Compound 220, 2.88 g, 8.50 mmol) in 10 mL Et3N and 20.0 mL DMF was sparged with argon for 10 minutes. To this solution was added trimethylsilylacetylene (4.15 g, 42.0 mmol) and bis(triphenylphosphine)-palladium(II) chloride (298.0 mg, 0.425 mmol). The solution was heated to 95° C. for 5 hours, cooled to room temperature, and diluted with H2O. Extraction with EtOAc was followed by washing the combined organic layers with H2O and saturated aqueous NaCl and drying over MgSO4. Concentration of the dry solution under reduced pressure and isolation of the product by column chromatography (3% EtOAc/hexanes) afforded 2.23 g (91%) of the title compound as an orange oil. 1H NMR (300 MHz, CDCl3) δ: 8.18 (1H, d, J=1.9 Hz), 7.34 (1H, dd, J=1.9, 8.1 Hz), 7.15 (1H, d, J=8.1 Hz), 2.85 (2H, s), 1.45 (6H, s), 0.23 (9H, s).

Workup

  1. temperaturecooled to room temperature
  2. extractionExtraction with EtOAc
  3. washby washing the combined organic layers with H2O and saturated aqueous NaCl
  4. dry with materialdrying over MgSO4

Sources & evidence

ORD record
ord-f907f2102c664d4bb6e2e7491b4c7d11
Source dataset
uspto-grants-1999_09
Patent number
US05958954

Reaction notes

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