Palladium‐Catalyzed Carbonylation of Allylic Chlorides to β,γ‐Unsaturated Esters/Amides under Mild Conditions

Improved procedures for carbonylative transformations (alkoxy‐ and aminocarbonylation) of cinnamyl chloride to synthesize β,γ‐unsaturated esters/amides have been developed. Studying critical reaction parameters (palladium precursors, solvents and bases) enabled the practical preparation of diverse β,γ‐unsaturated esters/amides under mild conditions (low Pd catalyst loading, phosphine‐free, 2 bar CO, 60 °C). The optimal catalytic system shows excellent chemo‐ and regioselectivity for the activation of the allylic C−Cl bonds. Efficient and convenient palladium‐catalyzed alkoxy‐ and aminocarbonylations of cinnamoyl chloride and aliphatic allyl chlorides to synthesize β,γ‐unsaturated esters/amides under mild condition were developed.