The Applications Of MCM-41-Supported Bidentate Phosphine Palladium(O) Catalysts And(E)-α-Iodovinylstannanes In Organic Synthesis

This dissertation consists of two parts:1. The applications of MCM-41-supported bidentate phosphine palladium(0) complex in C-C coupling reactions2. Stereoselective synthesis of difunctionalized 1,3–dienes containing tin and halogenPart one: The MCM-41-2P-Pd(0) complex shows high catalytic activity for Sonogashira cross-coupling of aryl iodides with (trimethylsilyl)acetylene,the products of Sonogashira cross-coupling can undergo a desilylation reaction with KF to afford a variety of substituted phenylacetylenes. The complex is also an efficient catalyst for the copper-free Stille cross-coupling of aryl halides with alkynylstannanes,vinylstannanes and arylstannanes in DMF/H2O under air. This palladium(0) complex catalyst can be easily recovered from the products and reused many times without loss of activity.Part two: (E)–α–Iodovinylstannanes undergo a direct coupling reaction with (trimethylsilyl)acetylene in the presence of [Pd(PPh3)4] and CuI catalysts in pyrrolidine to give (Z)–2-tributylstannyl-4–trimethylsilyl–1–buten–3–ynes, which can undergo a desilylation reaction in the presence of potassium fluoride to provide a practical route to the stereoselective synthesis of (Z)–2–tributylstannyl–1–buten–3–ynes.The hydrozirconation of (Z)–2–tributylstannyl–1–buten–3–ynes with Cp2Zr(H)Cl, followed by reacting with NBS or iodine, gave stereoselectively difunctionalized (E,Z)–1– halo–3–tributylstannyl–1,3–dienes.