Fluoroolefin dipeptide isosteres were synthesized applying the Peterson reaction as a novel for fluoroolefination. The dipeptide isosteres were elaborated to provide the conformationally constrained analogs (1-(R), 1-(S) and 2-(R), 2-(S)) of the Suc-Ala-Gly-Pro-Phe-pNA tetrapeptide, a synthetic substrate of cyclophilin.