The incorporation of fluorine atom into a stereogenic center is a highly challenging transformation with current methodologies offering access mainly to chiral alpha- and beta-fluoroalkanes. In this article, the development of a novel general approach to construct beta-, gamma-, delta-, and epsilon- fluoroalkanes with good enantioselectivity is described. Different directing groups, such as benzyl, ketone, and sulfonyl, were shown to give good enantioselectivity under Suzuki cross-coupling conditions in the presence of a Ni catalyst and chiral diamine ligand. It includes the first examples of enantioselective synthesis of chiral fluorine-containing centers at as distant as delta or epsilon positions from the functional groups.