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 alkeneisomerization 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 toacrylates.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.