Wang Kan, Bungard Christopher J, Nelson Scott G
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
Org Lett. 2007 Jun 7;9(12):2325-8. doi: 10.1021/ol0706511. Epub 2007 May 17.
Chemo- and stereoselective Ir(I)-catalyzed isomerization of 1,1-disubstituted and trisubstituted allylic ethers and in situ [3,3] sigmatropic rearrangement of the resulting allyl vinyl ethers provide for the highly stereoselective construction of quaternary carbon stereocenters. The olefin isomerization-Claisen rearrangement (ICR) sequence allows adjacent quaternary-tertiary stereocenter relationships to be established with excellent diastereoselection. Several complementary strategies for enantioselective quaternary carbon synthesis derive directly from the ICR reaction design.
化学和立体选择性的铱（I）催化1,1 - 二取代和三取代烯丙基醚的异构化以及所得烯丙基乙烯基醚的原位[3,3] - 西格玛重排为季碳立体中心的高度立体选择性构建提供了方法。烯烃异构化 - 克莱森重排（ICR）序列能够以优异的非对映选择性建立相邻的季碳 - 叔碳立体中心关系。几种对映选择性季碳合成的互补策略直接源于ICR反应设计。
