Divergent Synthesis of Trifluoromethyl Ketones via Photoredox Activation of Halotrifluoroacetones

Fluorine's high electronegativity, lipophilicity, and metabolic stability make it a valuable element for drug design and development. Consequently, significant synthetic efforts have focused on introducing fluorine and fluorinated motifs into organic molecules, with the synthesis of trifluoromethyl ketones (TFMKs) recently attracting considerable attention. Building on our ongoing research on radical organofluorine chemistry, we present herein the divergent synthesis of trifluoromethyl ketones directly from olefins using readily available chloro‐ and bromotrifluoroacetone as synthetic precursors of the trifluoroacetonyl radical under photoredox catalysis. Mechanistic studies revealed that the divergence is attained through radical polar crossover (RPC) and hydrogen atom transfer (HAT) mechanisms.