Comparison between Electron Transfer and Nucleophilic Reactivities of Ketene Silyl Acetals with Cationic Electrophiles
作者:Shunichi Fukuzumi、Kei Ohkubo、Junzo Otera
DOI:10.1021/jo005733g
日期:2001.2.1
d ketene silyl acetal (1: (Me2C=C(OMe)OSiMe3) with trityl cation salt (Ph3C+ClO4-) takes place between 1 and the carbon of para-positon of phenyl group of Ph3C+, whereas a much less sterically hindered ketene silyl acetal (3: H2C=C(OEt)OSiEt3) reacts with Ph3C+ at the central carbon of Ph3C+. The kinetic comparison indicates that the nucleophilic reactivities of ketene silyl acetals are well correlated
研究了酮甲硅烷基缩醛与一系列对甲氧基取代的三苯甲基阳离子反应的产物和动力学,并将其与由10,10'-二甲基-9,9进行的外球电子转移反应进行了比较。 ',10,10'-四氢-9,9'-二cr啶[(AcrH)2]形成相同系列的三苯甲基阳离子以及其他电子受体。β,β-二甲基取代的烯酮甲硅烷基缩醛(1:(Me2C = C(OMe)OSiMe3)与三苯甲基阳离子盐(Ph3C + ClO4-)的反应中的CC键形成在1和对位碳之间Ph3C +的苯基正位置,而空间位阻少得多的乙烯酮甲硅烷基乙缩醛(3:H2C = C(OEt)OSiEt3)在Ph3C +的中心碳上与Ph3C +反应。