Synthesis Of (E)-α-Iodovinyltellurides And (Z)-α-Arylsulfenylvinyltellurides And Their Applications In Highly Selective Synthetic Reactions

This dissertation describes the stereoselective synthesis of (E)-α-iodovinyltellurides and (Z)-α-arylsulfenylvinyltellurides and their applications as 1,1-difunctional group reagents in highly selective synthetic reactions.The acetylenic tellurides can be prepared by the reaction of the alkynyl Grignard reagents with tellurium, followed by traping the corresponding intermediates with alkyl halides or by the reaction of the alkynyl Grignard reagents in tetrahydrofuran at 0℃ under nitrogen with aryltellurenyl iodides in good yields. The hydro2:irconation of acetylenic tellurides with (Cp)₂Zr(H)Cl, and then the reaction with iodine, afforded stereoselectively (E)-α-iodovinyltellurides in good yields; or the reaction with arylsulfenyl chlorides, provided a new route to the stereoselective synthesis of (Z)-α-arylsulfenylvinyltellurides in good yields.We developed a novel approach to the stereoselective synthesis of (Z)-1,3-enynyltellurides by the crossed-coupling reaction of (E)-a-iodovinyltellurides and terminal alkynes in the presence of Pd(PPh₃)₄ and CuI. We also investigated the reaction of (E)-vinylzirconium complexes, which can be prepared by the reaction of terminal alkynes with (Cp)₂Zr(H)Cl, and (E)-α-iodovinyltellurides, providing a convenient approach to the stereoselective synthesis of (Z, E)-l,3-dienyltellurides.