Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, 29 Wangjiang Road, Chengdu, 610064, P. R. China.
Angew Chem Int Ed Engl. 2017 Oct 9;56(42):13094-13098. doi: 10.1002/anie.201708127. Epub 2017 Sep 11.
Described herein is the synthesis of stable oxonium-doped polycyclic aromatic hydrocarbons (PAHs) by the rhodium-catalyzed C-H activation/annulations of naphthalene-type aldehydes with internal alkynes. This protocol provides four divergent reaction types, including two unexpected annulations with an oxygen transposition process, which lead to diverse types of phenalenyl-fused pyrylium cations comprising a four-, five-, or six-ring-fused π-conjugated core. The annulations exhibit an exquisite regioselectivity and a high tolerance of sensitive functional groups. These PAHs feature intriguing photophysical properties such as full-color tunable fluorescence emission, high quantum yield, and positively charged core, and can be reduced easily to the phenalenyl radicals.
本文描述了通过铑催化的萘型醛与内炔的 C-H 活化/环化反应合成稳定的氧鎓掺杂多环芳烃（PAHs）。该方案提供了四种不同的反应类型，包括两个具有氧迁移过程的意外环化反应，生成了包含四、五或六元环稠合的π共轭核心的不同类型的菲并吡喃鎓阳离子。这些环化反应表现出极好的区域选择性和对敏感官能团的高容忍性。这些 PAHs 具有有趣的光物理性质，如全彩可调荧光发射、高量子产率和带正电荷的核心，并且可以很容易地还原为菲并自由基。
