【作者】 黄佳娣；

【导师】 蔡明中；

【作者基本信息】 江西师范大学 ， 有机化学， 2004， 硕士

【摘要】 本硕士论文由三部分组成： 第一部分：研究了钯催化下（E）-α-溴代烯基硒醚与烯基锆化合物的交叉偶联反应，提供了立体选择合成（Z，E）-2-硒芳基丁二烯的新途径。研究了钯催化下（E）-α-溴代烯基硒醚与Grignard试剂的交叉偶联反应，立体选择合成了（Z）-1，2-双取代烯基硒醚，后者在NiCl₂（PPh₃）₂催化下与Grignard试剂进行交叉偶联反应，提供了立体选择合成三取代烯烃的新途径。 第二部分：根据文献方法由炔基硅烷的锆氢化反应制备了（E）-α-硅基烯基锆化合物。研究了（E）-α-硅基烯基锆化合物与NBS或I₂的反应，立体选择性地合成了（E）-α-卤代烯基硅烷，后者在Pd（PPh₃）₄及CuI的催化下与端炔反应，提供了立体选择合成1，3-烯炔基硅烷的新方法。研究了（E）-α-硅基烯基锆化合物与ArTeI的反应，立体选择性地合成了（E）-α-硅基烯基碲醚，后者在NiCl₂（PPh₃）-2催化下与Grignard试剂进行交叉偶联反应，提供了立体选择合成（Z）-1，2-双取代烯基硅烷的新方法。 第三部分：根据文献方法由炔基锡烷的锆氢化反应制备了（Z）-α-锡基烯基锆化合物。研究了（Z）-α-锡基烯基锆化合物与ArTeI的反应，立体选择性地合成了（E）-α-芳碲基烯基锡烷，后者在Pd（PPh₃）₄及CuI的催化下与ArI进行交叉偶联反应，立体选择性地合成了（E）-1，2-双取代烯基碲醚，后者在NiCl₂（PPh₃）₂催化下与Grignard试剂进行交叉偶联反应，提供了立体选择合成三取代烯烃的又一新途径。更多还原

【Abstract】 This dissertation consists of three parts:Part one: We developed a novel approach to the stereoselective synthesis of (Z,E)-2-phenylselenobutadienes by the cross-coupling reaction of (E)-a-bromovinylselenides and alkenylzirconium complexes in the presence of palladium(0) catalyst. We found that (E)-a-bromovinylselenides underwent cross-coupling reactions with Grignard reagents catalyzed by tetrakis(triphenyl-phosphine)palladium(0) to give stereoselectively (Z)-1,2-disubstituted alkenyl-selenides, which can undergo NiCl2(PPh3)2-catalyzed cross-coupling reaction with Grignard reagents, providing a convenient approach to the stereoselective synthesis of trisubstituted alkenes.Part two: (E)-α-Silylvinylzirconium complexes were prepared by the hydr-ozirconation of alkynylsilanes with Cp2Zr(H)Cl. It was found that (E)-α-silylvinylzirconium complexes reacted with NBS or iodine to afford stereoselectively (E)-α-halovinylsilane, which were reacted with terminal acetylenes in the presence of Cul and Pd(PPh3)4, providing a convenient approach to the stereoselective synthesis of 1,3-enynylsilanes. (E)-α-Silylvinyl tellurides were synthesized stereoselectively via the hydrozirconation of alkynylsilanes, followed by the reaction with aryltellurenyl iodides. (E)-α-Silylvinyltellurides can undergo the cross coupling reaction with Grignard reagents in the presence of Ni(PPh3)2Cl2 catalyst to give (Z)-l,2-disubstituted vinylsilanes .Part three: (E)-α-Aryltellurenylvinylstannanes was synthesized stereo-s electively via the hydrozirconation of alkynylstannanes, followed by the reaction with aryltellurenyl iodides. (E)-α-Aryltellurenylvinylstannanes can react with aryl iodides in the presence of Cul and Pd(PPh3)4 to give (E)-1,2-di-s ubstituted vinyltellurides, which can undergo NiCl2(PPh3)2-catalyzed cross-coupling reaction with Grignard reagents, providing another convenient approach to the stereoselective synthesis of trisubstituted alkenes.更多还原