Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
J Am Chem Soc. 2010 Sep 1;132(34):11854-5. doi: 10.1021/ja1059119.
Addition of trimethylstannyllithium to a diarylacetylene takes place exclusively in an anti-fashion to produce a lithio vinylstannane intermediate. The regioselectivity of the addition is controlled by the steric and electronic property of the acetylene and reaches up to >99:1. The two newly 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.
三甲基锡锂加成到二芳基乙炔中，以反式构型进行，生成一个锂代乙烯基锡烷中间体。加成的区域选择性受乙炔的空间位阻和电子性质控制，最高可达>99:1。两个新形成的 C-金属键可以被顺序和立体特异性地转化为两个新的 C-C 键，如立体选择性合成 4-羟基他莫昔芬及其区域异构体所示。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，得到取代的二苯并[g,p]色烯衍生物。
