Triphenylphosphine → 4-[2-(Trimethylsilyl)ethynyl]pyridine-2-carbonitrile

HRID 447190

Reaction equation

HRID 447190 reaction equation
Br[C:2]1[CH:7]=[CH:6][N:5]=[C:4]([C:8]#[N:9])[CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:29][Si:30]([C:33]#[CH:34])([CH3:32])[CH3:31]>C1COCC1.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.[Cu]I>[CH3:29][Si:30]([C:33]#[C:34][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([C:8]#[N:9])[CH:3]=1)([CH3:32])[CH3:31]

Participants

7

Reactant 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 6932834-Bromo-2-cyanopyridine

Product 1

HCID 451164464-[2-(Trimethylsilyl)ethynyl]pyridine-2-carbonitrile

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

4-Bromo-2-pyridinecarbonitrile [Cesko-Slovenska Farmacie 25(5), 181 (1976)] (0.73 g, 4.0 mmol) was dissolved in 18 mL dry THF. This mixture was evacuated and backfilled with argon several times to remove oxygen from the solution. Triphenylphosphine (31 mg, 0.12 mmol) and bis(triphenylphosphine)palladium(II) chloride (141 mg, 0.20 mmol) were added and the reaction mixture was stirred at room temperature for 1 h. Copper(I) iodide (23 mg, 0.12 mmol) and trimethylsilyl-acetylene (590 mg, 6.0 mmol) were added. The reaction mixture was stirred at room temperature for 3 days. The solvent was evaporated. The residue was taken up in 100 mL water and extracted three times with 100 ml of ethyl acetate. The combined organic extracts were dried with magnesium sulfate, filtered and evaporated. The crude product was purified by flash chromatography on silica gel (heptane/methylene chloride 1:2). The desired product was obtained as a yellow oil (329 mg, 41%), MS: m/e=201.3 (M+H+).

Workup

  1. customThis mixture was evacuated
  2. customto remove oxygen from the solution
  3. stirringThe reaction mixture was stirred at room temperature for 3 days
  4. customThe solvent was evaporated
  5. extractionextracted three times with 100 ml of ethyl acetate
  6. dry with materialThe combined organic extracts were dried with magnesium sulfate
  7. filtrationfiltered
  8. customevaporated
  9. customThe crude product was purified by flash chromatography on silica gel (heptane/methylene chloride 1:2)

Sources & evidence

ORD record
ord-3bcc817320614321bba16dfb90d6a216
Source dataset
uspto-grants-2013_07
Patent number
US08481548B2

Linked notes

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