The Applications Of α-Halovinylstannanes In Highly Selective Synthetic Reactions And The Stereoselective Synthesis Of (E)-β-Arylsulfenylvinylic Selenides

Part one: This dissertation describes the synthesis of α-halovinylstannanes and their applications as 1,1-difunctional group reagents in highly selective synthetic reactions. The reactions of ethynyl Grignard reagent with chlorotrialkylstannanes gave the expected ethynylstannanes in good yields. The hydrozirconation of ethynylstannanes with (Cp)₂Zr(H)Cl gave α-stannylvinylzirconium complexes, which were treated with iodine or NBS, affording a new approach to synthesis of α-vinylstannanes. It was investigated that α-iodovinylstannanes underwent cross-coupling reactions with terminal alkynes in the presence of tetrakis(triphenylphosphine)palladium(0) and cuprous iodide, providing a new method to synthesize stereoselectively 1,3-enynylstannanes. Cross-coupling reactions of α-bromovinylstannanes with alkenylzirconium complexes catalyzed by tetrakis(triphenylphosphine)palladium(0) were investigated , which presented a novel approach to stereoselective synthesis of (3E)-l,3-dienylstannanes.Part two:We prepared ethynylarylselenides successfully by a simply way. The Hydrozirconation of ethynylarylselenides with (Cp)₂Zr(H)Cl , followed by reacting with arylsulfenyl chlorides , gave stereoselectively (E)-β-arylsulfenylvinylselenides, in good yields.