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The site‐selective palladium‐catalyzed three‐component coupling of unactivated alkenyl carbonyl compounds, aryl‐ or alkenylboronic acids, andN‐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 Pd^IVintermediate to afford 1,2‐carbofluorination products in moderate to good yields.

The site‐selective palladium‐catalyzed three‐component coupling of unactivated alkenyl carbonyl compounds, aryl‐ or alkenylboronic acids, andN‐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 Pd^IVintermediate to afford 1,2‐carbofluorination products in moderate to good yields.

Palladium(II)‐catalyzed C(alkenyl)−H alkenylation enabled by a transient directing group (TDG) strategy is described. The dual catalytic process takes advantage of reversible condensation between an alkenyl aldehyde substrate and an amino acid TDG to facilitate coordination of the metal catalyst and subsequent C(alkenyl)−H activation by a tailored carboxylate base. The resulting palladacycle then engages an acceptor alkene, furnishing a 1,3‐diene with high regio‐ andE/Z‐selectivity. The reaction enables the synthesis of enantioenriched atropoisomeric 2‐aryl‐substituted 1,3‐dienes, which have seldom been examined in previous literature. Catalytically relevant alkenyl palladacycles were synthesized and characterized by X‐ray crystallography, and the energy profiles of the C(alkenyl)−H activation step and the stereoinduction model were elucidated by density functional theory (DFT) calculations.

Palladium(II)‐catalyzed C(alkenyl)−H alkenylation enabled by a transient directing group (TDG) strategy is described. The dual catalytic process takes advantage of reversible condensation between an alkenyl aldehyde substrate and an amino acid TDG to facilitate coordination of the metal catalyst and subsequent C(alkenyl)−H activation by a tailored carboxylate base. The resulting palladacycle then engages an acceptor alkene, furnishing a 1,3‐diene with high regio‐ andE/Z‐selectivity. The reaction enables the synthesis of enantioenriched atropoisomeric 2‐aryl‐substituted 1,3‐dienes, which have seldom been examined in previous literature. Catalytically relevant alkenyl palladacycles were synthesized and characterized by X‐ray crystallography, and the energy profiles of the C(alkenyl)−H activation step and the stereoinduction model were elucidated by density functional theory (DFT) calculations.