Synthesis Of MCM-41-supported Phosphine And Mercapto Palladium Complexes And Their Application In Organic Synthesis

This dissertation consists of two parts:1. The synthesis of MCM-41-supported bidentate phosphine palladium complex and their applications in carbonylative cross-coupling reactions2. The synthesis of MCM-41-supported mercapto palladium complex and its catalytic property in the Stille coupling reaction of aryl halides with organostannanesPart one: Diphosphino-functionalized MCM-41 anchored palladium(II) complex (denoted as MCM-41-2P-Pd(II)) was conveniently synthesized from commercially available and cheapγ-aminopropyltriethoxysilane via immobilization on MCM-41, followed by reacting with diphenylphosphinomethanol and palladium chloride. The diphosphino-functionalized MCM-41 anchored palladium(0) complex(denoted as MCM-41-2P-Pd(0)) was also prepared by the reduction of MCM-41-2P-Pd(II) with hydrazine hydrate. The palladium complex was characterized by XRD, XPS and elemental analysis. It was found that MCM-41-2P-Pd(II) can efficiently catalyze the carbonylative Suzuki coupling of aryl iodides with arylboronic acids and the carbonylative cross-coupling of aryl halides with NaBPh4, giving a variety of monosubstituted or disubstituted diaryl ketones in good to high yields; We also found that the MCM-41-2P-Pd(0) exihibits high activity and selectivity in the carbonylative Stille coupling of aryl iodides with organostannanes, yielding a variety of unsymmetrical ketones in good to high yieds. The novel supported bidentate phosphine palladium catalyst can be easily recovered by simple filtration and can be reused many times without loss of activity.Part two: An MCM-41-supported mercapto palladium(0) complex was prepared fromγ-mercaptopropyltriethoxysilane via immobilization on MCM-41, followed by reacting with Me3SiCl and palladium chloride, then the reduction with hydrazine hydrate. It was found that this complex can efficiently catalyze the Stille coupling reaction of aryl halides with organostannanes, giving the corresponding coupled products in high yieds. This palladium(0) complex can be easily recovered from the products and reused many times without loss of activity.