New evidence on the regiochemistry of the tert-butyldiphenylsilylcupration of allene using the silylcuprate or silylcopper reagent
作者:Purificación Cuadrado、Ana M González-Nogal、Alicia Sánchez、M.Angeles Sarmentero
DOI:10.1016/s0040-4020(03)00945-1
日期:2003.7
ation of the allene depends on the temperature and also on the nature of the electrophile. Thus, the intermediate generated by addition of the silylcuprate at −78°C reacted with electrophiles to give allylsilanes, except with oxo compounds which afforded vinylsilanes. On the other hand, the silylcopper reagent was added at −40°C leading, in all cases, to the corresponding allylsilanes. When enones
丙二烯的叔丁基二苯基甲硅烷基杯中的区域化学取决于温度以及亲电试剂的性质。因此,在-78℃下通过添加甲硅烷基铜酸酯产生的中间体与亲电子试剂反应以产生烯丙基硅烷,除了与提供乙烯基硅烷的含氧化合物以外。另一方面,在所有情况下,在-40℃下将甲硅烷基铜试剂加入相应的烯丙基硅烷中。当烯酮用作亲电子试剂时,乙烯基硅烷是1,2-加成产物,烯丙基硅烷是1,4-加成产物。这些官能化的乙烯基或烯丙基叔-butyldiphenylsilanes是用于共轭的制备有趣合成子叔-丁基二苯基甲硅烷基三烯和官能化的环外亚烷基环戊烯。