6.1 Palladium-Catalyzed Dearomative Functionalization of Arenes

Abstract Palladium catalysis plays a pivotal role in organic synthesis, encompassing applications in cross-couplings and hydrogenations, among other transformations. Recent progress in palladium chemistry has helped enable catalytic dearomative functionalizations. In particular, catalysis involving benzyl–palladium species has been applied to achieve dearomative functionalization of a wide range of aromatic systems, including challenging substrates such as electronically unbiased benzenes, without the need to use an excess amount of the arene starting materials. This review primarily focuses on dearomative functionalization via benzyl–palladium species, incorporating applications of these methodologies in the synthesis of natural products.