Zhang Bo-Sheng, Jia Wan-Yuan, Gou Xue-Ya, Yang Ying-Hui, Wang Fan, Wang Yi-Ming, Wang Xi-Cun, Quan Zheng-Jun
Gansu International Scientific and Technological Cooperation Base of Water-Retention Chemical Functional Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China.
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, China.
Org Lett. 2022 Mar 25;24(11):2104-2109. doi: 10.1021/acs.orglett.2c00318. Epub 2022 Mar 15.
This report developed a method for the synthesis of C8-aminated pyrrolo-phenanthridines or -indoles by series C(sp)-H amination/ C(sp)-H or C(sp)-H arylation. N-benzoyloxyamines, as electrophilic amination reagents, did not undergo an electrophilic substitution reaction with the pyrrole side, but they did undergo a site-selective C-H amination reaction with the benzene side via Pd/NBE catalysis. The C8-aminated pyrrolo-phenanthridines have strong fluorescence in solution and solid state. X-ray single crystal diffraction shows that the steric hindrance of amino and benzene ring may inhibit aggregation-caused quenching (ACQ).
本报告开发了一种通过串联C(sp)-H胺化/C(sp)-H或C(sp)-H芳基化反应合成C8-胺化吡咯并菲啶或吲哚的方法。N-苯甲酰氧基胺作为亲电胺化试剂，不会与吡咯侧链发生亲电取代反应，但它们会通过Pd/NBE催化与苯侧链发生位点选择性C-H胺化反应。C8-胺化吡咯并菲啶在溶液和固态中都有很强的荧光。X射线单晶衍射表明，氨基和苯环的空间位阻可能会抑制聚集诱导猝灭（ACQ）。
