Air-Stable Palladium-Catalyzed Negishi Stille Coupling Reactions

General Procedure for Stille Couplings in Organic Solvent

A mixture of POPd (16.0 mg, 6 mol%) quinoline derivative (0.56 mmol), organostannane (0.7 mmol), and Cy2NMe (120 mg, 0.61 mmol) was stirred in 5 mL of anhydrous DMF at 135 oC for 24 h. The reaction mixture was allowed to cool to room temperature, quenched with water, and extracted with Et2O. The combined organic layers were washed with brine, dried over MgSO4, and the solvents were removed under vacuum. The residue was purified by flash chromatography on silica gel.

General Procedure for Stille Couplings in H2O

A mixture of POPd (16.0mg, 6mol%) aryl halide derivative (0.6mmol), phenyltrimethylstannane (0.7mmol), and Cy2NMe (120mg, 0.61mmol) was stirred in 5mL deionized water at 140oC using a closed vessel. After for 24h, the reaction mixture was allowed to cool to room temperature and extracted with Et2O. The combined organic layers were washed with brine, dried over MgSO4, and the solvents were removed under vacuum. The residue was purified by flash chromatography on silica gel.

References

1. Org. Biomol. Chem. 2004, 2, 2161-2164.
   Wolf,C. and Lerebours, R., "Palladium-Phosphinous Acid-Catalyzed Sonogashira Cross-Coupling Reactions in Water".
2. J. Org. Chem., 2003, 68(18), 7077-7084.
   Wolf, C. and Lerebours, R., "Using of Highly Active Palladium-phosphinous Acid Catalysts in Stille, Heck, Amination and Thiation Reactions of Chloroquinolines".
3. J. Org. Chem. 2003, 68(19), 7551-7554.
   Wolf, C. and Lerebours, R., "Efficient Stille Cross-Coupling Reaction Using Aryl Chlorides or Bromides in Water".
4. J. Org. Chem. 2001, 66(25), 8677-8681.
   Li, George Y.; Zheng, G.; Noonan, A. F. “Highly Active, Air-Stable Versatile Palladium Catalysts for the C-C, C-N, and C-S Bond Formations via Cross-Coupling Reactions of Aryl Chlorides”.