Department of Chemistry , The Scripps Research Institute , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States.
J Am Chem Soc. 2018 Sep 12;140(36):11317-11324. doi: 10.1021/jacs.8b05868. Epub 2018 Jul 26.
Alkene hydroarylation forms carbon-carbon bonds between two foundational building blocks of organic chemistry: olefins and aromatic rings. In the absence of electronic bias or directing groups, only the Friedel-Crafts reaction allows arenes to engage alkenes with Markovnikov selectivity to generate quaternary carbons. However, the intermediacy of carbocations precludes the use of electron-deficient arenes, including Lewis basic heterocycles. Here we report a highly Markovnikov-selective, dual-catalytic olefin hydroarylation that tolerates arenes and heteroarenes of any electronic character. Hydrogen atom transfer controls the formation of branched products and arene halogenation specifies attachment points on the aromatic ring. Mono-, di-, tri-, and tetra-substituted alkenes yield Markovnikov products including quaternary carbons within nonstrained rings.
烯烃氢芳基化在有机化学的两个基础构建块之间形成碳-碳键：烯烃和芳环。在没有电子偏见或导向基团的情况下，只有傅-克反应允许芳烃与烯烃以 Markovnikov 选择性反应，生成季碳原子。然而，碳正离子的中间体排除了使用缺电子的芳烃，包括路易斯碱性杂环。在这里，我们报告了一种高度 Markovnikov 选择性的双催化烯烃氢芳基化反应，它可以容忍任何电子特性的芳烃和杂芳烃。氢原子转移控制支化产物的形成，芳环的卤化指定了芳环上的连接点。单取代、二取代、三取代和四取代烯烃生成 Markovnikov 产物，包括非刚性环中的季碳原子。
