Perfluoroalkyl Editing of Fluoroalkynes: Chemo-, Regio-, and Stereoselective Synthesis of (<i>E</i>)-(2-Amino-fluoroalkenyl)pyrimidines

A chemo-, regio-, and stereoselective condensation reaction of perfluoroalkyl alkynes (PFAAs), (CH₂O)_n, and (NH₄)₂CO₃ through the cleavage of five inert C(sp³)-F bonds at three distinct carbon sites, thereby establishing an unprecedented platform for synthesizing structurally unique (<i>E</i>)-(2-amino-fluoroalkenyl)pyrimidines, is first developed. Remarkably, this reaction features mild reaction conditions, good compatibility with various functional groups, excellent <i>E</i>-stereoselectivity, late-stage modification of complex molecules, scalability, and versatile synthetic transformations of the resulting heterocyclic compounds.