Despite the undisputed importance of organofluorine compounds, for example, in biomedical applications, the generation of fluorinated carbon stereocenters by CΓF bond-forming reactions remains rare and particularly challenging. [1, 2] Recently, the first catalytic, enantioselective fluorination of b-ketoesters with F-TEDA (1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane; TEDA triethylenediamine) in the presence of 5 % of [TiCl 2 (TADDOLato)] (TADDOL a,a,a',a'-tetraaryl-2,2-dimethyl-1,3-dioxolan-4,5dimethanol) catalysts was reported. [3, 4] We have shown that the reaction proceeds smoothly in acetonitrile at room temperature and the obtained enantioselectivity reaches 90 % ee using a (R,R)-TADDOL bearing 1-naphthyl substituents. [4] We assume, as a first mechanistic hypothesis, that mass spectrometer source with a syringe pump (Harvard type 55 1111: Harvard Apparatus Inc., South Natick, MA, USA) with a flow rate of 4 mL min Γ1 . Calibration was performed using protonated horse myoglobin. Scanning was performed in the MCA (multichannel analyzer) mode, and several scans were combined to obtain the final spectrum. Electrochemical studies were made by cyclic voltammetry with a conventional threeelectrode system using a BAS CV-50 W voltammetric analyzer equipped with a Pt microdisk or a Hg Kemula hanging electrode as working electrode and a Ag wire counter electrode. Ferrocene (E 1/2 0.65 V) or paraquat (E 1/2 Γ 0.23 and Γ 0.60 V) were used as an internal standard with the Pt and Hg electrodes, respectively. Solutions contained the electrode-active substrate (ca. 5 Γ 10 Γ4 mol dm Γ3 ) in deoxygenated and anhydrous DMF containing tetra-N-butylammonium tetrafluoroborate (0.2 mol dm Γ3 ) as supporting electrolyte. The quoted half-wave potentials were reproducible within 15 mV.