The Study On Copper Catalyzed Cross-Couping Reactions

Recently, copper-catalyzed cross coupling reactions have become a focus of research on catalytically organic synthesis. Derived from readily available o-bromobenzaldehyde, oxime-phosphine oxide 28 was synthesized according to an improved methodology, and was applied to copper-mediated C(aryl)-S bond formation. A high catalytic activity was observed. Using CuI as catalyst, ligand 28 could successfully catalyze the coupling of various aryl iodides with primary alkyl thiols or aryl mercaptan, and high yields were obtained.Using CuI as catalyst, bisphenols were studied as ligands in copper-catalyzed C(aryl)-N coupling reaction. Among the bisphenols studied, rac-BINOL was found to show optimal activity in the coupling reaction between iodobenzene and morphine. Under optimized conditions, rac-BINOL/Cu powder could efficiently catalyze the coupling of aryl iodides with primary amines or cyclic secondary amines. When a mixture of Cu powder and CuI were used as catalyst, rac-BINOL can efficiently catalyze the coupling of various aryl bromides with primary amines especially with benzyl amine and good to excellent yields were provided. Apart from alkyl amines, many aryl bromides, even heterochorides could be efficiently coupled by N-H heterocycles.With the property of high efficiency and high stability, oxime-phosphine 28 was a very good candidate in C(aryl)-S bond formation. Meanwhile, the use of efficient and readily available rac-BINOL with good stability as well as mild...