Abstract The substrate range of the [TiCl 2 (TADDOLate)](TADDOL= α, α, α′, α′-tetraaryl- 1, 3-dioxolane-4, 5-dimethanol)-catalyzed asymmetric α-fluorination of activated β-carbonyl compounds has been investigated. Optimal conditions for catalysis are characterized by using 5 mol-% of TiCl 2 (naphthalen-1-yl)-TADDOLate) as catalyst in a saturated (0.14 mol/l) MeCN solution of F-TEDA (1-(chloromethyl)-4-fluoro-1, 4-diazoniabicyclo [2.2. 2] octane ...