School of Chemistry, Engineering Research Center of Energy Storage Materials and Devices, Ministry of Education, Xi'an Key Laboratory of Sustainable Energy Materials Chemistry, Xi'an Jiaotong University, Xi An Shi, Xi'an, 710049, China.
Frontier Institute of Science and Technology, Xi'an Jiaotong University, Xi An Shi, Xi'an, 710049, China.
Angew Chem Int Ed Engl. 2023 Jun 5;62(23):e202302835. doi: 10.1002/anie.202302835. Epub 2023 May 3.
Both organic radicals and organoboron reagents have been broadly investigated, but the combination of them via direct C-H borylation as organic radical building blocks has never been achieved. Herein, a series of organoradical boron reagents, such as TTM-Bpin and TTM-BOH, were synthesized through the key step of C-H borylation of substrate TTM-H ((2,6-dichlorophenyl) bis(2,4,6-trichlorophenyl)methyl) radical for the first time. They are air stable enough to be stored in the solid state for several months under dark conditions, and fully investigated through single crystal analysis, EPR and DFT calculations. Furthermore, they can smoothly work in the standard Suzuki-Miyaura coupling (SMC) reaction with retention of the carbon radical center. Meanwhile, these radical species bearing different boron units display fluorescent character and are potentially applied for the collective synthesis of luminescent organic radicals, as well as other functionalized open-shell materials.
有机自由基和有机硼试剂都得到了广泛的研究，但它们通过直接 C-H 硼化作为有机自由基构建块的组合从未实现过。在此，通过底物 TTM-H((2,6-二氯苯基)双(2,4,6-三氯苯基)甲基)自由基的 C-H 硼化的关键步骤，首次合成了一系列有机自由基硼试剂，如 TTM-Bpin 和 TTM-BOH。它们在空气中足够稳定，可以在黑暗条件下以固态形式储存数月，并且通过单晶分析、EPR 和 DFT 计算进行了充分研究。此外，它们可以在保留碳自由基中心的情况下顺利进行标准的 Suzuki-Miyaura 偶联（SMC）反应。同时，这些带有不同硼单元的自由基具有荧光特性，可用于集体合成发光有机自由基以及其他功能化的开壳材料。
