Xiong Wei, Jiang Xuan, Wang Wen-Cheng, Cheng Ying, Lu Liang-Qiu, Gao Ke, Xiao Wen-Jing
CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan 430079, P. R. China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, 345 Lingling Road, Shanghai 200032, P. R. China.
J Am Chem Soc. 2023 Apr 12;145(14):7983-7991. doi: 10.1021/jacs.2c13538. Epub 2023 Mar 28.
Conjugate addition is among the most important synthetic protocols for constructing carbon skeletons and is widely used to synthesize natural products and drugs. However, asymmetric catalysis studies have mainly focused on constructing stereogenic centers arising from conjugate alkenes. Here, we report the first photoinduced cobalt-catalyzed dynamic kinetic reductive conjugate addition reaction that enables the formation of heterobiaryls with axial chirality (45 examples, up to 91% yield and 97% ee). This method features mild reaction conditions, good functional-group tolerance, and excellent enantiomeric control. Significantly, large amounts of metal waste and precious metal catalysts can be avoided under these conditions. Migration of the chiral arylcobalt species into the alkene might be the rate-determining step based on kinetic studies.
共轭加成是构建碳骨架最重要的合成方法之一，被广泛用于天然产物和药物的合成。然而，不对称催化研究主要集中于构建由共轭烯烃产生的手性中心。在此，我们报道了首例光诱导钴催化的动态动力学还原共轭加成反应，该反应能够形成具有轴手性的杂联芳基（45个实例，产率高达91%，对映体过量值高达97%）。该方法具有反应条件温和、官能团耐受性好以及对映体控制优异的特点。值得注意的是，在这些条件下可以避免产生大量金属废料和贵金属催化剂。基于动力学研究，手性芳基钴物种向烯烃的迁移可能是速率决定步骤。
