Photoinduced Cobalt‐Catalyzed Synthesis of Allylic/Homoallylic Trifluoromethylated Compounds From Alkenes

Developing practical strategies to produce high‐value trifluoromethyl‐containing chemicals such as pharmacologically active molecules, from bulk starting materials remains an ongoing challenge. One potential route to this goal is the modification of simple double bonds using synthons that contain trifluoromethyl groups. However, previous methods for introducing trifluoromethyl groups still suffer from limitations, as they can only afford terminal allylic trifluoromethylated structures. Herein, we report a strategy for the synthesis of allylic and homoallylic trifluoromethylated compounds from simple alkenes using photomediated, biomimetic cobalt complex catalysis. This strategy employs α‐iodotrifluoromethylalkanes as the source of trifluoromethyl radicals and takes advantage of their structural diversity for further derivatization, thereby overcoming the limitation of previous methods that could only afford terminal allylic trifluoromethylated structures. This low‐cost and operationally simple protocol exhibits good yields in scale‐up reactions under mild conditions, features broad substrate scope, and holds potential value for pharmaceutical applications.