Sodium Carbonate → 3-Bromo-5-thiophen-3-yl-pyridine

HRID 1385993Notes

Reaction equation

HRID 1385993 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([Br:8])[CH:7]=1.[S:9]1[CH:13]=[CH:12][C:11](B(O)O)=[CH:10]1.C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.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>[Br:8][C:6]1[CH:5]=[N:4][CH:3]=[C:2]([C:11]2[CH:12]=[CH:13][S:9][CH:10]=2)[CH:7]=1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 693693,5-DibromopyridineHCID 581760Thiophene-3-boronic acid

Product 1

HCID 112764923-Bromo-5-thiophen-3-yl-pyridine

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

A deoxygenated solution of 3,5-dibromopyridine (4.00 g, 16.9 mmol, 1 equiv), 3-thiopheneboronic acid (2.38 g, 18.6 mmol, 1.10 equiv), Pd(PPh3)4 (781 mg, 0.676 mmol, 0.0433 equiv), and 2.0 M Na2CO3 (16.9 mL, 33.8 mmol, 2.00 equiv) in dioxane (40 ml) was heated under argon at reflux for 20 h. The reaction mixture was allowed to cool, then partitioned between water (200 mL) and ethyl acetate (2×300 mL). The combined organic layers were dried over sodium sulfate and concentrated. The residue was purified by flash column chromatography (5% ethyl acetate in dichloromethane) to afford 3-bromo-5-thiophen-3-yl-pyridine as a white solid.

Workup

  1. temperatureat reflux for 20 h
  2. temperatureto cool
  3. custompartitioned between water (200 mL) and ethyl acetate (2×300 mL)
  4. dry with materialThe combined organic layers were dried over sodium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified by flash column chromatography (5% ethyl acetate in dichloromethane)

Sources & evidence

ORD record
ord-894d7d9f6cbf461b80a5bbec4d00673a
Source dataset
uspto-grants-2001_07
Patent number
US06265403B1

Reaction notes

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