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TCI Practical Example: Ullmann-type Coupling Reaction Using N,N'-Bis(2-phenyl-1-naphthyl)-1,2-benzenediamine

We are proud to present the Ullmann-type coupling reaction of 3-bromoquinoline and 1-butanol using N,N'-bis(2-phenyl-1-naphthyl)-1,2-benzenediamine as a catalytic ligand. This reaction has the advantage of proceeding at room temperature.

Used Chemicals

• 3-Bromoquinoline [B1013]
• 1-Butanol [B0704]
• N,N'-Bis(2-phenyl-1-naphthyl)-1,2-benzenediamine [B6801]
• Copper(I) Iodide [C2163]
• Sodium tert-Butoxide [S0450]
• DMSO

Procedure

3-Bromoquinoline (300 mg, 1.44 mmol), 1-butanol (160 µL, 1.73 mmol), N,N'-bis(2-phenyl-1-naphthyl)-1,2-benzenediamine (74.0 mg, 144 µmol), copper(I) iodide (13.7 mg, 72.1 µmol) and sodium tert-butoxide (277 mg, 2.88 mmol) were dissolved in DMSO (2 mL) and stirred at room temperature for 1.5 hours. The reaction was quenched with water and the aqueous layer was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and filtered. The solvent was removed under reduced pressure and the residue was purified by silica gel column chromatography (ethyl acetate:hexane = 0:100 - 5:95) to give 3-butoxyquinoline as a yellow oil (227 mg, 78% yield).

Experimenter’s Comments

The reaction mixture was monitored by NMR.
The reaction was carried out under a nitrogen atmosphere.

Analytical Data

3-Butoxyquinoline

¹H NMR (270 MHz, CDCl₃); δ 8.65 (d, J = 3.0 Hz, 1H), 8.02 (dd, J = 6.8, 1.1 Hz, 1H), 7.70 (dd, J = 6.2, 1.9 Hz, 1H), 7.56-7.45 (m, 2H) 7.35 (d, J = 2.7 Hz, 1H), 4.07 (t, J = 6.5 Hz, 2H), 1.90-1.79 (m, 2H), 1.60-1.47 (m, 2H), 0.99 (t, J = 7.6 Hz, 3H).

Lead Reference

• Activation of Aryl Chlorides for Suzuki Cross-Coupling by Ligandless, Heterogeneous Palladium
  • M. J. Strauss, M. E. Greaves, S. T. Kim, C. N. Teijaro, M. A. Schmidt, P. M. Scola, S. L. Buchwald, Angew. Chem. Int. Ed. 2024, 63, e202400333.

Other References

• Cu-Catalyzed Amination of Base-Sensitive Aryl Bromides and the Chemoselective N- and O-Arylation of Amino Alcohols
  • M. J. Strauss, K. X. Liu, M. E. Greaves, J. C. Dahl, S. T. Kim, Y. J. Wu, M. A. Schmidt, P. M. Scola, S. L. Buchwald, J. Am. Chem. Soc. 2024, 27, 18616.