Pent-4-en-1-amines are reactive to fluoroalkyl iodides with respect to sodium dithionite initiated free radical addition reactions. We report here the development of a novel and efficient synthesis of 2-fluoroalkyl pyrrolidine derivatives by sodium dithionite initiated one-pot reaction of pent-4-en-1-amines bearing various protecting groups with fluoroalkyl iodides. Among which, the N-benzyl-pent-4-en-1-amine