The reaction of 1-fluorooctane (1) with an excess of lithium powder (4-10 equiv.) and DTBB (2-4 equiv.) in THP at 0 o C for 5 min gives a solution of the corresponding 1-octyllithium (2), which reacts then with different electrophiles at 0 o C (D 2 O, MeSiCl, Bu t CHO, Et 2 CO), or -78 o C [ClCO 2 Me, (PhCH 2 S) 2 ] or -40 o C (CO 2 ) to room temperature to give, after hydrolysis, the expected products (3). The same process applied to 2-fluorooctane gives mainly octane as reaction product, independently on the electrophile used, resulting from a proton abstraction by 2-lithiooctane formed from the reaction medium before addition of the electrophilic reagent.