Hydrosilylation of α,β-unsaturated nitriles and esters catalyzed by tris (triphenylphosphine)chlororhodium
作者:Iwao Ojima、Miyoko Kumagai、Yoichiro Nagai
DOI:10.1016/s0022-328x(00)87057-6
日期:1976.5
trichlorosilane which afforded β-adduct with acrylonitrile. On the other hand, the hydrosilylation of α,β-unsaturated esters gave rather complex results. The selectivity of the reactions was dramatically affected by the substituent of the ester group and that on the β-carbon. Thus, the hydrosilylation of ethyl acrylate with triethylsilane afforded a β-adduct, but, that of ethyl crotonate using the same hydrosilane
描述了使用三(三苯基膦)氯铑作为催化剂的α,β-不饱和腈和酯的氢化硅烷化,例如丙烯腈,巴豆腈,肉桂腈,丙烯酸乙酯和甲基丙烯酸酯,巴豆酸乙酯和甲基丙烯酸甲酯以及甲基丙烯酸乙酯和甲基丙烯酸甲酯。α,β-不饱和腈的氢化硅烷化仅以高收率提供α-加合物,除了三氯硅烷的情况下,其提供了带有丙烯腈的β-加合物。另一方面,α,β-不饱和酯的氢化硅烷化产生相当复杂的结果。反应的选择性受酯基的取代基和β-碳上的取代基的影响很大。因此,丙烯酸乙酯与三乙基硅烷的氢化硅烷化得到β-加合物,但是使用相同的氢化硅烷的巴豆酸乙酯的氢化硅烷化仅得到1,4-加合物。