Combining Fluoroalkylation and Defluorination to Enable Formal [3 + 2 + 1] Heteroannulation by Using Visible-Light Photoredox Organocatalysis.

A metal-free, visible-light photoredox-catalyzed three-component [3 + 2 + 1] heteroannulation for accessing modular fluoroalkylated pyrimidines from readily available silyl enol ether, amidine, and fluoroalkyl halide is developed. This protocol distinguishes itself by broad functional group tolerance in a regioselective manner, which provides a complement to the existing methods for the construction of pharmaceutically and biologically active organofluorine compounds.