Photocatalytic Synthesis and Palladium‐Catalyzed Functionalizations of Hydrofluoroolefin (HFO‐1234ze)‐Based Vinyl Iodides

The utilization of low‐impact industrial refrigerants as chemical feedstocks offers a highly sustainable pathway for the synthesis of complex organofluorine compounds. Herein, we report a scalable methodology to access a novel fluoroalkyl iodide building block directly from commercially available HFO‐1234ze gas under green, solvent‐free conditions. To overcome the inherent kinetic stability of this specific fluoroalkyl iodide isomer, we developed an efficient, visible‐light‐induced atom transfer radical addition to terminal alkynes utilizing the metal‐free organic dye 4CzIPN as a photocatalyst. The protocol exhibits broad functional group tolerance and reveals distinct, substrate‐dependent stereochemical preferences. The synthetic utility of the resulting fluorous vinyl iodides was demonstrated through modular diversification via palladium‐catalyzed Sonogashira and Suzuki cross‐coupling reactions, providing access to a diverse library of trifluoromethylated conjugated alkenes.