Ligand‐Controlled Switchable Synthesis of Fused Polycycles by Selective 1,4‐Palladium Migration

ABSTRACT The palladium migration strategy has been employed for the functionalization of remote C─H bonds, offering an efficient approach to construct fused heterocycles. In this study, a novel ligand‐controlled switchable synthesis of fused quinolinone skeletons from 1,7‐enynes and perfluoroalkyl iodides via selective 1,4‐palladium migration is disclosed. When DPEphos is used as the ligand, vinyl‐to‐aryl 1,4‐palladium migration is promoted, affording a wide range of perfluoroalkyl‐containing 4,5,10‐fused quinolinone derivatives. In contrast, the use of DPPPy as the ligand facilitates vinyl‐to‐alkyl 1,4‐palladium migration, yielding various perfluoroalkyl‐containing 3,4‐fused quinolinone derivatives. Notably, this protocol also enables modifications of various drug molecules. DFT calculations have been conducted to elucidate the cis‐trans isomerization pathways of alkenyl palladium intermediates with different ligands.