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A photo‐induced indole 2‐alkylation reaction was developed with unactivated stereo‐congested alkenes used as the Friedel–Crafts alkylation reagent. The neutral, traceless and inexpensive perfluoroalkyl iodide C4F9I was used as the radical initiator in catalytic amount under irradiation by a blue LED light. Brønsted acids are in situ generated from the radical transfer reactions between the indole...
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