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

HRID 2112811Notes

Reaction equation

HRID 2112811 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 are 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 is stirred for 30 minutes at 0° C. The reaction mixture is stirred for a further 3.5 hours at RT, then filtered, and the filtrate is evaporated down in vacuo. The residue is dissolved in 1 L of EtOAc, and the organic phase is washed with water and saturated NaCl solution, dried over sodium sulfate (Na2SO4), and evaporated down in vacuo. The crude product is further reacted 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 is stirred for a further 3.5 hours at RT
  2. filtrationfiltered
  3. customthe filtrate is evaporated down in vacuo
  4. dissolutionThe residue is dissolved in 1 L of EtOAc
  5. washthe organic phase is washed with water and saturated NaCl solution
  6. dry with materialdried over sodium sulfate (Na2SO4)
  7. customevaporated down in vacuo
  8. customThe crude product is further reacted without purification

Sources & evidence

ORD record
ord-206884768716404896ed0a5b6288d2b2
Source dataset
uspto-grants-2009_04
Patent number
US07524862B2

Reaction notes

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