Photocatalytic Divergent Trifluoromethylthiolation of N ‐Sulfonylacrylamides Enabling Access to SCF 3 ‐Substituted Alkenes and Oxindoles

The divergent construction of molecules with a trifluoromethylthio group addresses significant synthetic challenges and is highly desirable in organic chemistry. Herein, we report a photocatalytic, metal and oxidant‐free, practical, and efficient strategies for divergent trifluoromethylthiolation of N ‐sulfonylacrylamides to the synthesis of synthetically useful vinyl trifluoromethylthioethers (via Heck coupling) and trifluoromethylthiolated oxindoles (via Smiles rearrangement). This divergent transformation occurred smoothly, driven by different reaction conditions, enabling achievement of Heck coupling and cascade rearrangement reactions, respectively. This protocol provides a mild and efficient strategy to access synthetically valuable trifluoromethylthiolated molecules from readily available chemicals.