Selective addition of hydrosilanes to 1,3-dienes catalyzed by polyamide-supported metal complex catalysts
作者:Zofia M. Michalska、Bogdan Ostaszewski、Krzysztof Strzelec
DOI:10.1016/0022-328x(95)05469-6
日期:1995.6
hydrosilylations catalyzed by polymer-supported rhodium catalysts, the 1,4 mode of addition prevailed with HSiMe2Ph, but 1,2 addition with HSi(EtO)3. Essentially the same regioselectivity was found for reactions under the homogeneous conditions. These results demonstrated that the microporous structure of the polyamide supports did not exert any particular effect on the regioselective and stereoselective course
四个过渡金属络合物[RhCl(CO)2 ] 2,PdCl 2(PhCN)2,PtCl 2(PhCN)2和RuCl 2(bipy)2固定在具有吡啶部分重复单元且相对均匀的聚酰胺上孔隙从1.0到3.0 nm的微孔分布。为了研究聚合物形态对催化剂选择性的影响,将聚合物负载的催化剂用于异戊二烯和2-甲基-1,3-戊二烯的硅氢加成反应。HSiMe 2 Ph和HSi(EtO)3的添加被聚合物负载的Rh(I)催化剂催化的1,3-二烯的合成反应被发现可以高度区域选择性和立体选择性地进行,得到(Z)-(2-甲基-丁烯-en-2-en-1-基)硅烷和(Z)-(2-甲基-戊-2-烯-1-基)硅烷为主要产物(85-95%)。产物的立体化学归属是利用核Overhauser效应通过1 H NMR光谱进行的。发现将Me 2 PhSiH与异戊二烯和2-甲基-1,3-戊二烯进行类似的1,4-加成反应,可制得Z异构体,作为聚