Triphenylphosphine → 2-Chloro-4-(2-(trimethylsilyl)ethynyl)pyridine

HRID 447220Notes

Reaction equation

HRID 447220 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6](I)[CH:5]=[CH:4][N:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:28][Si:29]([C:32]#[CH:33])([CH3:31])[CH3:30]>C1COCC1.C(N(CC)CC)C.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>[Cl:1][C:2]1[CH:7]=[C:6]([C:33]#[C:32][Si:29]([CH3:31])([CH3:30])[CH3:28])[CH:5]=[CH:4][N:3]=1

Participants

8

Reactant 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 15165112-Chloro-4-iodopyridine

Product 1

HCID 219853912-Chloro-4-(2-(trimethylsilyl)ethynyl)pyridine

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

2-Chloro-4-iodo-pyridine (10.0 g, 41.8 mmol) was dissolved in 200 mL dry THF and 17.5 mL triethyl amine. This mixture was evacuated and backfilled with argon several times to remove oxygen from the solution. Triphenylphosphine (329 mg, 1.25 mmol) and bis(triphenylphosphine)palladium(II) chloride (1.47 g, 2.09 mmol) were added and the reaction mixture was stirred at room temperature for 1 h. Copper(I) iodide (239 mg, 1.25 mmol) and trimethylsilylacetylen (6.28 g, 6.39 mmol) were added. The reaction mixture was stirred at room temperature overnight. The solvent was evaporated. The residue was taken up in 500 mL water and extracted three times with ethyl acetate (500 mL each). The combined organic extracts were dried with magnesium sulfate, filtered and evaporated. The crude product was purified by chromatography on silica gel (cyclohexane/ethyl acetate 80:20). The desired product was obtained as a light brown semi solid (10 g, >100%). This material was used without any further purification for the next step.

Workup

  1. customThis mixture was evacuated
  2. customto remove oxygen from the solution
  3. stirringThe reaction mixture was stirred at room temperature overnight
  4. customThe solvent was evaporated
  5. extractionextracted three times with ethyl acetate (500 mL each)
  6. dry with materialThe combined organic extracts were dried with magnesium sulfate
  7. filtrationfiltered
  8. customevaporated
  9. customThe crude product was purified by chromatography on silica gel (cyclohexane/ethyl acetate 80:20)

Sources & evidence

ORD record
ord-85194f790e4748cd8cef8b1cf9ceda4c
Source dataset
uspto-grants-2013_07
Patent number
US08481548B2

Reaction notes

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