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Condensation of Hörner–Wadsworth–Emmons reagents 3 and ketones 2 with a perfluoroalkyl (Rf) moiety prepared in situ was proved to be significantly efficient and powerful methods for the construction of a wide variety of α,β-unsaturated esters with Rf and R1 groups both at the β-position due to convenient avoidance of usually tedious as well as troublesome isolation steps of these ketones 2.