Copper-Catalyzed Cross-Coupling Reactions

This dissertation includes the copper-catalyzed Suzuki-Miyaura cross-coupling reaction, the Sonogashira C-C cross-coupling reaction and the Buchwald-Hartwig N-arylations reaction.1. Progress in copper-catalyzed cross-coupling reactions, invovling the Suzuki-Miyaura cross-coupling reaction, the Sonogashira cross-coupling reactions and the Buchwald-Hartwig N-arylation reaction, were described. In this chapter, effects of the copper catalyst, ligand, and media on the copper-catalyzed cross-coupling reactions were discussed in detail.2. CuI combined with DABCO (1,4-diaza-bicyclo[2.2.2]octane) was developed as an inexpensive and efficient catalytic system for the Suzuki-Miyaura cross-coupling of vinyl halides with arylboronic acids. In presence of TBAB, the couplings between vinyl iodides with arylboronic acids catalyzed by catalytic amounts of CuI and DABCO were carried out smoothly in moderate to excellent yields. Moreover, the catalytic system was found to be efficient for the Sonogashira coupling reactions of vinyl halides with terminal alkynes.3. TBAB (tetra-n-butylammonium bromide) was found to improve the ligand-free copper-catalyzed cross-couplings of aryl halides with arylboronic acids. In the presence of 10 mol% of CuI and 20 mol% of TBAB, a variety of aryl halides underwent the coupling with arylboronic acids smoothly to afford the corresponding products in moderate to good yields.4. Copper-catalyzed N-arylation of nitrogen-containing heterocycle compounds with aryl halides has been developed. In the presence of CuI, POPh₃ and TBAF, imidazoles and triazoles underwent the N-arylation reaction with a variety of aryl halides smoothly in good yields. It is noteworthy that the reaction was conduct under solvent-free conditions.5. Palladium-catalyzed C-H bond activation reactions of N-methyl-1H-imidazole with aryl halides have been developed under solvent-free condition. In the presence of Pd(OAc)₂, POPh₃, and TBAF, the reaction of various aryl halides with N-methyl-1H-imidazole was conducted successfully in good yields under solvent-free condition.