S1 Visible-Light-Promoted Cascade Alkene Trifluoromethylation and Dearomatization of Indole Derivatives via Intermolecular Charge Transfer Min Zhu, †,‡ Kai Zhou, † Xiao Zhang,* ,† and Shu-Li You* ,†,‡ † State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China ‡ School of Physical Science and Technology, ShanghaiTech University, 100 Haike Road, Shanghai 201210, China Table of Contents 1. General methods ........................................................................................................ 2 2. Detailed screening of reaction conditions .................................................................. 3 3. Reaction details and characterization data ................................................................. 4 4. Transformations of 3a .............................................................................................. 26 5. Experimental details for mechanistic studies ........................................................... 29 6. X-Ray crystal data of 3a (minor isomer) ................................................................. 34 7. Copies of NMR spectra............................................................................................ 37