A Sterically Tuned Directing Auxiliary Promotes Catalytic 1,2‐Carbofluorination of Alkenyl Carbonyl Compounds

The site‐selective palladium‐catalyzed three‐component coupling of unactivated alkenyl carbonyl compounds, aryl‐ or alkenylboronic acids, and N‐fluorobenzenesulfonimide is described herein. Tuning of the steric environment on the bidentate directing auxiliary enhances regioselectivity and facilitates challenging C(sp3)−F reductive elimination from a PdIV intermediate to afford 1,2‐carbofluorination products in moderate to good yields. Judicious tuning of the steric environment on the bidentate directing auxiliary is proposed to facilitate challenging C(sp3)−F reductive elimination from a PdIV intermediate in the site‐selective palladium‐catalyzed three‐component coupling of unactivated alkenyl carbonyl compounds, aryl‐ or alkenylboronic acids, and N‐fluorobenzenesulfonimide.