Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, No. 100, Shiquan First Road, Sanmin District, Kaohsiung City 807, Taiwan.
Department of Medical Research, Kaohsiung Medical University Hospital, No. 100, Tzyou First Road, Sanmin District, Kaohsiung City 807, Taiwan.
Org Lett. 2020 Oct 16;22(20):7848-7852. doi: 10.1021/acs.orglett.0c02739. Epub 2020 Oct 6.
Unprecedented chemo- and regioselective synthesis of benzo[]fluorenes and naphthamide-substituted benzo[]fluorenes were constructed from the reaction of ()-2-aroyl-3-(2-(arylalkynes/alkenes)aryl)acrylonitrile scaffolds under metal-free conditions via the activation of nitriles and alkenes, respectively. A tentative reaction mechanism was proposed for this homofunctionalization of nitriles. Control experiments showed that the reaction proceeds via selective nitrile or alkene protonation, depending upon the substrates. Additionally, we demonstrated an alternative expeditious route for the synthesis of disubstituted benzo[]fluorenes in the presence of TfOH alone.
从（）-2-芳基-3-（2-（芳基炔烃/烯烃）芳基）丙烯腈支架的反应出发，在无金属条件下，分别通过腈和烯烃的活化，构建了前所未有的苯并[]荧光酮和萘甲酰胺取代的苯并[]荧光酮的区域和化学选择性合成。提出了一种用于此类腈的同官能化的推测反应机理。控制实验表明，反应通过选择性腈或烯烃质子化进行，具体取决于底物。此外，我们还展示了在单独存在三氟甲磺酸的情况下合成二取代苯并[]荧光酮的另一种快捷途径。
