Arene-catalysed lithiation of phenyl- and 1,1-diphenylcyclopropane: synthetic applications
作者:Cecilia Gómez、Victor J. Lillo、Miguel Yus
DOI:10.1016/j.tet.2007.03.102
日期:2007.5
crowded ketones γ-products 11 are isolated, for aldehydes and non-congested ketones α-products 10 are formed. The application of the same protocol to 1,1-diphenylcyclopropane (7) leads to a mixture of products 13–15 resulting from the introduction of one or two electrophilic fragments to the open-chain mono- or dilithiated intermediate: also in this case the regiochemistry of the reaction is governed
室温下,苯基环丙烷(1)与过量的锂和催化量的DTBB(2.5%摩尔)在THF中反应,然后用亲电试剂[Me 3 SiCl,PhMe 2 SiCl,t- BuCHO,PhCHO, Me 2 CO,Et 2 CO,(CH 2)5 CO,金刚烷-2-酮,i -Pr 2 CO,二(环丙基)酮]并最终用水水解会生成烯丙基产物10或11,具体取决于亲电子试剂:而对于氯硅烷或拥挤的酮,γ-产物11分离出醛和醛,形成非浓缩的酮α-产物10。相同的协议,以1,1- diphenylcyclopropane(应用程序7)导致的产物的混合物13 - 15从导入一个或两个亲电片段,以开链单-或二锂化中间体得到的:在此情况下的反应的区域化学由空间原因决定。