S2 Table of Contents 1. General Information ....................................................................................................................... 3 2. Starting Material Synthesis ............................................................................................................. 4 3. Procedure for synthesis of [Cu(dap)2]Cl .......................................................................................... 5 4. Synthesis and Cyclic voltammetry of phenyl-λ3-iodanediyl bis(2-fluoroacetate) ........................... 6 5. Optimization of the reaction conditions ......................................................................................... 8 6. Mechanistic investigation ............................................................................................................. 11 7. General procedure for oxy-monofluoromethylation of alkenes .................................................. 22 8. Scale up Experiment...................................................................................................................... 23 9. Characterization data.................................................................................................................... 24 10. Identification of by-product as an impurity in isolated products ............................................. 39 11. X-ray crystal structure of compound (3aq) ............................................................................... 40 12. Further functionalization of products ....................................................................................... 42 13. Scope of the iodine(III) reagent (1) in synthesizing –CH2F containing heterocycles ................ 44 14. References ................................................................................................................................ 46 15. Copies of 1H, 19F and 13C spectra ............................................................................................... 47