Synthesis of Tetrasubstituted Alkenes by Stereo- and Regioselective Stannyllithiation of Diarylacetylenes
作者:Hayato Tsuji、Yasuyuki Ueda、Laurean Ilies、Eiichi Nakamura
DOI:10.1021/ja1059119
日期:2010.9.1
formed C-metal bonds can be sequentially and stereospecifically transformed into two new C-C bonds as illustrated by stereoselective synthesis of 4-hydroxytamoxifen and its regioisomer. A tetraarylethene bearing different aryl groups can be synthesized similarly and cyclized to a substituted dibenzo[g,p]chrysene derivative via a palladium-catalyzed arylation reaction.
三甲基锡锂与二芳基乙炔的加成仅以反方式发生以产生锂硫乙烯基锡烷中间体。加成的区域选择性受乙炔的空间和电子性质控制,最高可达 >99:1。如 4-羟基三苯氧胺及其区域异构体的立体选择性合成所示,两个新形成的 C-金属键可以依次立体定向地转化为两个新的 CC 键。带有不同芳基的四芳基乙烯可以类似地合成并通过钯催化的芳基化反应环化为取代的二苯并[g,p]芘衍生物。