Substrate-Controlled Relay Carbonylation Coupled with Regioselective C=C Isomerization

Selective carbonylation coupled with C=C isomerization enables the efficient synthesis of carbonyl frameworks. Yet precisely controlling relay carbonylation and regioselective alkene isomerization within a single catalytic system remains a key challenge. Herein, we show that switching the allylic heteroatom from N to O shifts Pd intermediate formation from cyclic to acyclic, owing to O's weaker σ-donation ability and reduced chelating capability. The flexible acyclic intermediate favors β-H elimination, thereby triggering isomerization and delivering acrylates in high yield with excellent selectivity. The methodology delivers outstanding atom and step economy and tolerates a broad range of functional groups, providing a practical and sustainable route to acrylates. Mechanistic studies reveal that ligand-substrate cooperativity modulates the electrophilicity of the π-allylpalladium, thereby dictating pathway selection. This provides both mechanistic insight and design principles for relay carbonylation.