Ethyl Acetate → 5-Bromo-2-((tert-butyldimethylsilyl)ethynyl)pyridine

HRID 734777Notes

Reaction equation

HRID 734777 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][N:3]=1.[C:9]([Si:13]([C:16]#[CH:17])([CH3:15])[CH3:14])([CH3:12])([CH3:11])[CH3:10].CCOC(C)=O>C1COCC1.C(N(CC)CC)C.[Cu]I>[Br:8][C:5]1[CH:6]=[CH:7][C:2]([C:17]#[C:16][Si:13]([C:9]([CH3:12])([CH3:11])[CH3:10])([CH3:15])[CH3:14])=[N:3][CH:4]=1

Participants

7

Reactant 3

HCID 8857Ethyl AcetateHCID 693532,5-DibromopyridineHCID 2757281(tert-Butyldimethylsilyl)acetylene

Product 1

HCID 666112135-Bromo-2-((tert-butyldimethylsilyl)ethynyl)pyridine

Reagents, catalysts & solvents 3

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

Conditions

Temperature
0 °C

Procedure

Under an argon atmosphere 0.80 g (4.20 mmol) of CuI and 2.90 g (4.13 mmol) of bis(triphenylphosphane)palladium (II) chloride were added to a solution of 49.90 g (201.0 mmol) of 2,5-dibromopyridine and 43.0 mL (225.6 mmol) of tert-butylethynyldimethylsilane in 500 mL of dry THF and 120 mL of triethylamine at −7° C. and the mixture was stirred for 30 minutes at 0° C. The reaction mixture was stirred for a further 3.5 hours at RT, then filtered and the filtrate was evaporated down in vacuo. The residue was dissolved in 1 L of EtOAc, the organic phase was washed with water and saturated NaCl solution, dried over sodium sulfate, and evaporated down in vacuo. The crude product was reacted further without purification. Yield: 59.5 g (quant. yield); C13H18BrNSi (M=296.278); calc.: molpeak (M+H)+: 296/298 (Br); found: molpeak (M+H)+: 296/298 (Br); Rf value: 0.75 (silica gel, cyc/EtOAc 8:1).

Workup

  1. stirringThe reaction mixture was stirred for a further 3.5 hours at RT
  2. filtrationfiltered
  3. customthe filtrate was evaporated down in vacuo
  4. dissolutionThe residue was dissolved in 1 L of EtOAc
  5. washthe organic phase was washed with water and saturated NaCl solution
  6. dry with materialdried over sodium sulfate
  7. customevaporated down in vacuo
  8. customThe crude product was reacted further without purification

Sources & evidence

ORD record
ord-5ddbae0132af472593118cea696e65f6
Source dataset
uspto-grants-2009_09
Patent number
US07592358B2

Reaction notes

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