2-Bromopyridine → HCID 66598649, compound

HRID 1189331Notes

Reaction equation

HRID 1189331 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1.[Cl:8][C:9]1[CH:14]=[CH:13][C:12]([N:15]([C:23](=[O:28])[CH2:24][CH2:25][C:26]#[CH:27])[C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[CH:11][CH:10]=1>C(N(CC)CC)C.[Cu]I.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>[Cl:8][C:9]1[CH:10]=[CH:11][C:12]([N:15]([C:23](=[O:28])[CH2:24][CH2:25][C:26]#[C:27][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=2)[C:16](=[O:22])[O:17][C:18]([CH3:19])([CH3:20])[CH3:21])=[CH:13][CH:14]=1

Participants

6

Reactant 2

HCID 79732-BromopyridineHCID 86630254HCID 86630254, compound

Product 1

HCID 66598649HCID 66598649, compoundYield 55%

Reagents, catalysts & solvents 3

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

Conditions

Temperature
0 °C

Procedure

To a solution of CuI (7.7 mg, 0.041 mmol) in triethylamine (2.28 mL) were added 2-bromopyridine (129 mg, 0.82 mmol) and (PPh3)2PdCl2 (28.7 mg, 0.041 mmol). The reaction mixture was cooled to 0° C. and tert-butyl 4-chlorophenyl(pent-4-ynoyl)carbamate (250 mg, 0.82 mmol) was added. The reaction mixture was allowed to warm to room temperature and then heated under reflux for 3 h. at 70° C. Triethylamine was evaporated, water was added and the aqueous phase was extracted twice with DCM. The organic phase was dried over Na2SO4, filtered and concentrated. The crude residue was purified by flash chromatography (prepacked 25 g silicagel column, Cyclohexane/AcOEt:70/30 as eluent) to afford 172 mg (Yield: 55%) of tert-butyl 4-chlorophenyl(5-(pyridin-2-yl)pent-4-ynoyl)carbamate as a yellow oil.

Workup

  1. temperatureto warm to room temperature
  2. temperatureheated
  3. temperatureunder reflux for 3 h. at 70° C
  4. customTriethylamine was evaporated
  5. additionwater was added
  6. extractionthe aqueous phase was extracted twice with DCM
  7. dry with materialThe organic phase was dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude residue was purified by flash chromatography (prepacked 25 g silicagel column, Cyclohexane/AcOEt:70/30 as eluent)

Sources & evidence

ORD record
ord-0432fc34d71b4ce7b6fe0f892c6f291d
Source dataset
uspto-grants-2014_03
Patent number
US08674106B2

Reaction notes

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