Polyarylquinones have found a lot of applications in optoelectronics, photocatalysis, bioimaging, and pharmaceutically relevant materials. However, their synthesis is often challenging and plagued with various bottleneck steps. Here, we demonstrate a relayed addition of fulvene moieties onto quinones. The developed ligand-assisted Pd-catalyzed dehydrogenative [2 + 2 + 2] cycloaddition reaction enables facile access to a new class of polyarylquinones. The key to achieving a high regioselectivity is the precisely controlled addition of the two fulvene units to the quinone conferred by the Pd catalyst. The work also establishes the broad substrate scope of the reaction and delves into the mechanism of the dehydrogenative coupling reaction. Moreover, single-crystal X-ray diffraction reveals interesting packing motifs suggesting the suitability of these materials in optoelectronics. As a practical utilization of the reaction, various synthesized polyarylquinones with structural diversity were screened for their redox properties and found to exhibit better antioxidant or chemotherapeutic properties.

The transition metal‐catalyzed CH bond functionalization has been achieved by various catalytic processes, among which copper‐catalyzed reactions have emerged as an environmentally benign and economical alternative. Here, an attempt has been made to collate all the seminal reactions based on CH functionalization to construct CC bond since 2012. This article discusses the evolution of this field from its nascent stages, where strategies for simple activation of sp, sp 2 , and sp 3 CH bonds of pronucleophiles were explored, to the more recent site‐selective reactions. In past decades, many bidentate ligands, for example amino acids, diamines, fused pyridines, oxazolidinones, and amides have transformed the Cu‐catalyzed coupling reactions into a practical and versatile synthetic tool. While the examples have been described with details about reaction conditions, some insight into the mechanistic pathways has also been presented.

A practical and straightforward protocol to access site-selective C-3 phosphorylated benzofulvenes by means of cross-dehydrogenative coupling of two nucleophilic moieties, employing silver as a promoter, is described here. Remark-ably, this protocol provides a broad, structurally diverse phosphorylated benzofulvene. Initial mechanistic studies shed light on its radical coupling nature, and late-stage transformations offer highly diversified benzofulvenes core.