Li Bo, Xing Donghui, Li Xiaohong, Chang Shunqin, Jiang Huanfeng, Huang Liangbin
State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, Guangdong 510640, People's Republic of China.
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, Guangdong 510641, People's Republic of China.
Org Lett. 2023 Sep 15;25(36):6633-6637. doi: 10.1021/acs.orglett.3c02396. Epub 2023 Sep 6.
Herein, we report a light-driven, radical-type cyano migration in the absence of a photocatalyst, enabling a chemo-divergent synthesis of ()-alkenyl nitriles and ketones. Trifluoromethyl thianthrenium salt (TT-CFOTf) plays multiple roles: (a) absorbing light to generate trifluoromethyl radicals to initiate the reaction and (b) forming α-thianthrenium cyano species by capture of TT . ()-Alkenyl nitriles were formed through the elimination of thianthrenium salts, and aryl ketones were obtained via the nucleophilic substitution of thianthrenium salts.
在此，我们报道了在无光催化剂的情况下光驱动的自由基型氰基迁移反应，实现了（）-烯基腈和酮的化学发散合成。三氟甲基噻蒽盐（TT-CFOTf）发挥多种作用：（a）吸收光以产生活性三氟甲基自由基引发反应，以及（b）通过捕获TT形成α-噻蒽氰基物种。（）-烯基腈通过噻蒽盐的消除反应生成，芳基酮则通过噻蒽盐的亲核取代反应得到。
