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TCI Practical Example: Suzuki-Miyaura Coupling Using Ni(COD)₂

We are proud to present the Suzuki-Miyaura cross coupling reaction of 4'-chloroacetophenone with phenylboronic acid using Ni(COD)₂. Ni(COD)₂ may be partially discolored since it is unstable in the air, but it has been confirmed that there is no problem in its functionality through this experiment.

Used Chemicals

• 4'-Chloroacetophenone [C0033]
• Phenylboronic Acid [B0857]
• Bis(1,5-cyclooctadiene)nickel(0) (= Ni(cod)₂) [B6553]
• Triphenylphosphine [T0519]
• Tripotassium Phosphate
• THF

Procedure

Phenylboronic acid (366 mg, 3.0 mmol, 1.5 eq.), triphenylphosphine (42 mg, 0.16 mmol, 0.08 eq.), tripotassium phosphate (1.27 g, 6.0 mmol, 3.0 eq.) and Ni(COD)₂ (22 mg, 0.08 mmol, 0.04 eq.) were weighed and sealed in a glove box. 4'-Chloroacetophenone (0.26 mL, 2.0 mmol) in THF (8 mL) was added to this mixture. The reaction mixture was stirred for 24 hours at room temperature, and then quenched with water (15 mL). The solution was extracted with ethyl acetate (15 mL x 3) and the combined organic layer was washed with brine (15 mL), dried over sodium sulfate and filtered. The solvent was removed under reduced pressure and the residue was purified by column chromatography (on silica gel, ethyl acetate:hexane = 1:10) to give 4-acetylbiphenyl as a white solid (360 mg, 92% yield).

Experimenter's Comments

The reaction mixture was monitored by GC.
Commercially available dry THF was used.
The functionality of the partially discolored Ni(cod)₂ was verified, and it was confirmed through this experiment that the reaction proceeded without any problems.

Analytical Data

4-Acetylbiphenyl

¹H NMR (400 MHz, CDCl₃); δ 8.04 (d, J = 8.0 Hz, 2H), 7.69 (d, J = 8.0 Hz, 2H), 7.63 (d, J = 7.2 Hz, 2H), 7.50-7.46 (m, 2H), 7.42-7.39 (m, 1H), 2.65 (s, 3H).

Lead Reference

• Triphenylphosphine as a Ligand for Room-Temperature Ni(0)-Catalyzed Cross-Coupling Reactions of Aryl Chlorides with Arylboronic Acids
• • Z.-Y. Tang, Q.-S. Hu, J. Org. Chem. 2006, 71, 2167.