【作者】 叶红德；

【导师】 蔡明中；

【作者基本信息】 江西师范大学 ， 有机化学， 2003， 硕士

【摘要】 本论文工作设计合成了1，1-双官能团试剂——α-卤代烯基锡烷，继而研究了它们在烯烃立体选择合成反应中的应用。 由炔基Grignard试剂与三烃基氯化锡反应高产率地制备了炔基锡烷，后者与Cp₂Zr（H）Cl反应之后再分别与I₂或NBS反应，提供了立体选择合成（E）-α-碘代烯基锡烷和（Z）-α-溴代烯基锡烷的方法。研究了（E）-α-碘代烯基锡烷在Pd（PPh₃）₄催化下与Grignard试剂的交叉偶联反应，立体选择性地合成了（Z）-1，2-双取代烯基锡烷，后者在Pd（PPh₃）₄和CuI催化下与碘代芳烃进行交叉偶联反应，提供了立体选择合成三取代烯烃的新途径。研究了（E）-α-碘代烯基锡烷在Pd（PPh₃）₄和CuI催化下与端炔的交叉偶联反应，提供了立体选择合成（Z）-1，3-烯炔基锡烷的新途径。研究了（Z）-α-溴代烯基锡烷在Pd（PPh₃）₄催化下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）-1，3-共轭二烯基锡烷的新途径。更多还原

【Abstract】 This dissertation describes the stereoselective synthesis of a - halovinylstan-nanes and their application as 1,1 - difunctional group reagents in stereoselective synthesis of alkenes.The reactions of alkynyl Grignard reagents with chlorotributylstannane gave the expected alkynylstannanes in good yields, the latter reacted with Cp2Zr(H)Cl and then with iodine or NBS, respectively, affording a new approach to stereoselective synthesis of (E) - a - iodovinylstannanes and (Z) - a - bromovinyl-stannanes.It was found that (E) - a - iodovinylstannanes underwent cross - coupling reactions with Grignard reagents catalyzed by tetrakis(triphenylphosphine) palladium(0) to give stereoselectively (Z) - 1,2 - disubstituted vinylstannanes, which were cross - coupled with aryl iodine in the presence of tetrakis ( triph-enylphosphine) palladium (0) and cuprous iodide, providing a novel method to synthesize stereoselectively trisubstituted alkenes. It was investigated that (E) - a - 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 (Z) - 1,3 - enynylstan-nanes. Cross - coupling reactions of ( Z) - a - bromovinylstannanes with alkenylzirconium complexes in the presence of tetrakis(triphenylphosphine) palladium(0) were investigated, which presented a novel approach to stereoselective synthesis of(Z,E)- 1,3 - dienylstannanes.更多还原