Photochemical carbon-silicon bond forming reaction on electron-deficient alkenes by disilanes and polysilanes via photoinduced electron transfer
作者:Kazuhiko Mizuno、Kazuhisa Nakanishi、Jun-ichi Chosa、Yoshio Otsuji
DOI:10.1016/0022-328x(94)80103-7
日期:1994.6
of electron-deficient alkenes with disilanes in acetonitrile gave silylated alkanes in high yields. The photosilylation occurred in a highly regioselective manner at the position β to the electron-withdrawing groups of the alkenes. With asymmetrically substituted disilanes and polysilanes, silyl groups bearing more bulky substituents were preferentially introduced to the alkenes. The photoreactions were
缺电子的烯烃与乙硅烷在乙腈中的菲敏光反应可得到高产率的甲硅烷基化的烷烃。在烯的吸电子基团的位置β处以高度区域选择性的方式发生光硅烷化。对于不对称取代的乙硅烷和聚硅烷,优选将带有更大体积取代基的甲硅烷基引入烯烃中。光反应被芳香烃(如菲和苯并菲)敏化,但不被pyr或蒽敏化。在没有芳族烃的情况下,光反应是不明显的。光反应的关键步骤是与甲硅烷基自由基的缺电子烯烃与自由基阴离子的反应,它们是由乙硅烷和聚硅烷的自由基阳离子的亲核试剂裂解产生的。讨论了光反应的机理。