Grimaldi Tamiris B, Lutz Guilherme, Back Davi F, Zeni Gilson
Laboratório de Síntese, Reatividade, Avaliação Farmacológica e Toxicológica de Organocalcogênios, CCNE, UFSM, Santa Maria, Rio Grande do Sul 97105-900, Brasil.
Laboratório de Materiais Inorgânicos, CCNE, UFSM, Santa Maria, Rio Grande do Sul, 97105-900, Brazil.
Org Biomol Chem. 2016 Nov 8;14(44):10415-10426. doi: 10.1039/c6ob01807f.
In this paper, we report our results on the cyclization of (biphenyl-2-alkyne) derivatives to give two different types of phenanthrene derivatives, 9-iodo-10-organochalcogen-phenanthrenes and 9-organochalcogen-phenanthrenes. The strategy for the synthesis was based on the use of electrophilic cyclization for the preparation of 9-iodo-10-organochalcogen-phenanthrenes and iron(iii) chloride/diorganyl diselenide-mediated intramolecular cyclization to prepare 9-organochalcogen-phenanthrenes. The effects of solvent, temperature, reaction time and stoichiometry on the efficiency of cyclization reactions were investigated. The standard reaction conditions were compatible with many functional groups in the substrates, such as methyl, chlorine, fluorine and methoxyl. This protocol was efficient for diorganyl diselenides and disulfides but ineffective for diorganyl ditellurides. The resulting phenanthrenes were further functionalized through Sonogashira reactions followed by the electrophilic cyclization reaction to give the selenophene-fused aromatic compounds.
在本文中，我们报告了关于（联苯 - 2 - 炔）衍生物环化生成两种不同类型菲衍生物，即9 - 碘 - 10 - 有机硫属元素菲和9 - 有机硫属元素菲的结果。合成策略基于使用亲电环化制备9 - 碘 - 10 - 有机硫属元素菲，以及使用氯化铁（III）/二有机二硒化物介导的分子内环化制备9 - 有机硫属元素菲。研究了溶剂、温度、反应时间和化学计量比对环化反应效率的影响。标准反应条件与底物中的许多官能团兼容，如甲基、氯、氟和甲氧基。该方法对二有机二硒化物和二硫化物有效，但对二有机二碲化物无效。所得菲通过Sonogashira反应进一步官能化，然后进行亲电环化反应，得到硒吩稠合的芳香族化合物。
