Two types of allylic trifluoromethylated compounds were synthesized by reacting alkynes with CF3CH2I using visible-light photocatalysis. Subtle differences in the catalytic system controlled the selectivity of iodotri...Two types of allylic trifluoromethylated compounds were synthesized by reacting alkynes with CF3CH2I using visible-light photocatalysis. Subtle differences in the catalytic system controlled the selectivity of iodotrifluoroethy- lation and hydrotrifluoroethylation. The iodotrifluoroethylated products were obtained in the presence of [Ru（bpy）3]C12 and TMEDA in CH3CN under visible-light irradiation, whereas hydrotrifluoroethylated products were synthesized usingfac-[Ir（ppy）3] and a mixture of DBU and K2CO3 in DMF. The iodotrifluoroethylation reac- tion worked particularly well, even at gram-scale, and the synthetic utility of iodotrifluoroethylated products was proved by their coupling reactions, providing complex CF3-containing products.展开更多
Internal alkynes are widespread skeletons in bioactive molecules and materials which are also used as important building blocks in chemical synthesis. Herein, we report a novel and efficient copper-catalyzed Sonogashi...Internal alkynes are widespread skeletons in bioactive molecules and materials which are also used as important building blocks in chemical synthesis. Herein, we report a novel and efficient copper-catalyzed Sonogashira reaction between sulfonium salts and alkynes through an anti-Markovnikov ring-opening pathway promoted by visible light. The coexistence of the nitrogen and phosphorus ligands in the system is the key to the success of this reaction. This radical type ring-opening reaction affords a new strategy for the synthesis of internal alkynes. Furthermore, this study is also an effective complement to the diverse reaction patterns of sulfonium salts.展开更多
文摘Two types of allylic trifluoromethylated compounds were synthesized by reacting alkynes with CF3CH2I using visible-light photocatalysis. Subtle differences in the catalytic system controlled the selectivity of iodotrifluoroethy- lation and hydrotrifluoroethylation. The iodotrifluoroethylated products were obtained in the presence of [Ru（bpy）3]C12 and TMEDA in CH3CN under visible-light irradiation, whereas hydrotrifluoroethylated products were synthesized usingfac-[Ir（ppy）3] and a mixture of DBU and K2CO3 in DMF. The iodotrifluoroethylation reac- tion worked particularly well, even at gram-scale, and the synthetic utility of iodotrifluoroethylated products was proved by their coupling reactions, providing complex CF3-containing products.
基金supported by the National Natural Science Foundation of China(22271170)the Scientific Research Foundation of Qingdao University of Science and Technology(1203043003457).
文摘Internal alkynes are widespread skeletons in bioactive molecules and materials which are also used as important building blocks in chemical synthesis. Herein, we report a novel and efficient copper-catalyzed Sonogashira reaction between sulfonium salts and alkynes through an anti-Markovnikov ring-opening pathway promoted by visible light. The coexistence of the nitrogen and phosphorus ligands in the system is the key to the success of this reaction. This radical type ring-opening reaction affords a new strategy for the synthesis of internal alkynes. Furthermore, this study is also an effective complement to the diverse reaction patterns of sulfonium salts.
