Grupo de Lactamas y Heterociclos Bioactivos, Departamento de, Química Orgánica I, Unidad Asociada al CSIC, Facultad de Química, Universidad Complutense de Madrid, 28040, Madrid, Spain.
Instituto de Química Orgánica General, Consejo Superior de Investigaciones Científicas, IQOG-CSIC, Juan de la Cierva 3, 28006, Madrid, Spain.
Chemistry. 2018 Jun 7;24(32):8186-8194. doi: 10.1002/chem.201800630. Epub 2018 May 14.
Functionalized ynones can be activated by Tf C=CH , which was generated in situ, to form zwitterionic species. These species were trapped in an intramolecular fashion by several nucleophiles to generate two major types of triflones in a divergent manner. Through fine-tuning of the reaction temperature, bis(triflyl)-6-membered- or (triflyl)-5-membered-fused-heterocycles were achieved in reasonable yields in a totally selective manner. In this way, bis(triflyl)flavones, bis(triflyl)thioflavones, bis(triflyl)selenoflavones, (triflyl)benzothienopyrans, (triflyl)benzoselenophenopyrans, (triflyl)vinyl aurones, and (triflyl)pyranoindoles were constructed. Conceivable mechanistic pathways were suggested on the basis of the isolation of several intermediates and the results from control experiments.
功能化的 ynones 可以被原位生成的 Tf C=CH 激活，形成两性离子物种。这些物种通过几种亲核试剂以分子内的方式捕获，以发散的方式生成两种主要类型的三氟酮。通过精细调节反应温度，可以以完全选择性的方式以合理的产率获得双（三氟甲基）-6 元环或（三氟甲基）-5 元环稠合杂环。通过这种方式，构建了双（三氟甲基）黄酮、双（三氟甲基）硫代黄酮、双（三氟甲基）硒代黄酮、（三氟甲基）苯并噻吩并吡喃、（三氟甲基）苯并硒吩并吡喃、（三氟甲基）乙烯基奥酮和（三氟甲基）吡喃并吲哚。根据几种中间体的分离和对照实验的结果，提出了可以想象的反应机制途径。
