Metal-catalyzed silacyclopropanation of mono- and disubstituted alkenes
Metal-catalyzed silacyclopropanation of mono- and disubstituted alkenes
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DOI：
10.1021/ja020566i
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发表时间：
2002-08-14
影响因子：
15
通讯作者：
Woerpel, KA
中科院分区：
文献类型：
--
作者：
Cirakovic, J;Driver, TG;Woerpel, KA
作为形成硅环丙烷所需的强还原条件的替代，硅烯转移被开发为一种温和的、耐官能团的硅环丙烷合成方法。以环己烷二叔丁基硅环丙烷1为原料，由官能化的烯烃合成了复杂的硅环丙烷。通过使用催化量的金属盐，可以从1生成二叔丁基硅烯。在−为27℃时，三氟化银以立体选择性和非对映选择性催化1-丁二硅烯向单取代和双取代烯烃的转移。用催化溴化锌和甲酸甲酯原位官能化硅环丙烷，可以方便地从烯烃一瓶合成复杂的硅环戊烷。
As an alternative to the strongly reducing conditions necessary for the formation of silacyclopropanes, silylene transfer was developed as a mild, functional group tolerant method of silacyclopropanation. Complex silacyclopropanes were formed from functionalized alkenes using cyclohexane di-tert-butyl silacyclopropane,1,as the source oft-Bu2Si. Di-tert-butyl silylene can be generated from1through the use of a catalytic amount of a metal salt. At −27 °C, silver triflate catalyzes the transfer oft-Bu2Si from1to mono- and disubstituted alkenes stereospecifically and diastereoselectively. In situ functionalization of silacyclopropanes with catalytic zinc bromide and methyl formate provides for an expedient one-flask synthesis of complex oxasilacyclopentanes from alkenes.