3-Bromopyridine → HCID 69588948, compound

HRID 2212133Notes

Reaction equation

HRID 2212133 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:12][CH2:11][CH2:10][C@H:9]1[C:13]#[CH:14])=[O:7])([CH3:4])([CH3:3])[CH3:2].Br[C:16]1[CH:17]=[CH:18][CH:19]=[N:20][CH:21]=1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[Cu]I>[C:1]([O:5][C:6]([N:8]1[CH2:12][CH2:11][CH2:10][C@H:9]1[C:13]#[C:14][C:18]1[CH:19]=[N:20][CH:21]=[CH:16][CH:17]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 2

HCID 122863-BromopyridineHCID 11030701(S)-N-Boc-2-ethynylpyrrolidine

Product 1

HCID 69588948HCID 69588948, compoundYield 71.7%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 167845palladium(II) acetateCatalystHCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
60 °C

Procedure

Triethylamine (10 mL) was degassed by bubbling argon over a period of 30 min. (S)-N-(tert-butoxycarbonyl)-2-ethynylpyrrolidine (1.00 g, 5.12 mmol), tetrakis(triphenylphosphine)palladium (0.296 g, 0.256 mmol), palladium(II) acetate (0.0575 g, 0.256 mmol), copper (I) iodide (16.2 mg, 0.085 mmol) and 5-bromopyridine (2.43 g, 15.4 mmol) were added. The mixture was heated at 60° C. for 24 h, then cooled to room temperature and concentrated by rotary evaporation. The residue was dissolved in chloroform (50 mL) and the organic phase washed sequentially with water (25 mL), saturated aqueous NaHCO3 solution (3×20 mL) and water (25 mL). The solution was then dried (MgSO4), filtered and concentrated by rotary evaporation. The crude product was purified by column chromatography on silica gel, eluting with ethyl acetate/hexane (1/1, v/v). Selected fractions containing the product were concentrated via rotary evaporation to give 1.00 g (71%) of a yellow oil.

Workup

  1. customTriethylamine (10 mL) was degassed
  2. additionwere added
  3. temperaturecooled to room temperature
  4. concentrationconcentrated by rotary evaporation
  5. dissolutionThe residue was dissolved in chloroform (50 mL)
  6. washthe organic phase washed sequentially with water (25 mL), saturated aqueous NaHCO3 solution (3×20 mL) and water (25 mL)
  7. dry with materialThe solution was then dried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated by rotary evaporation
  10. customThe crude product was purified by column chromatography on silica gel
  11. washeluting with ethyl acetate/hexane (1/1
  12. additionSelected fractions containing the product
  13. concentrationwere concentrated via rotary evaporation

Sources & evidence

ORD record
ord-562d03d5575f4c84b6ba3bea496dad0c
Source dataset
uspto-grants-2006_09
Patent number
US07101896B2

Reaction notes

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