Palladium‐Catalyzed Enantioselective Four‐Component Carbonylative Dicarbofunctionalization of Internal Alkenes With 1 Atm CO

ABSTRACT Transition metal‐catalyzed carbonylation employing CO as a C1 feedstock is fundamental for synthesizing carbonyl compounds in industrial/fine chemical synthesis. Despite the ubiquity of chiral carbonyl motifs in bioactive molecules, general methods for catalytic asymmetric carbonylation under mild conditions remain scarce, hindered by stereocontrol challenges and competing pathways. Current approaches often rely on multistep sequences or restrictive intramolecular strategies. Herein, we report palladium‐catalyzed intermolecular four‐component carbonylative dicarbofunctionalization of internal alkenes, aryl diazonium salts, and nucleophiles under 1 atm CO. This method enables simultaneous control over regio‐, diastereo‐, and enantioselectivity, efficiently constructing congested vicinal stereocenters in acyclic chiral carbonyl scaffolds. Nucleophile modularity affords diverse enantioenriched esters or ketones in high yields and stereoselectivity. The mild conditions prevent racemization of chiral carbonyls, and derivatizations highlight broad synthetic utility.