We report the first example of Pd(II)catalyzed highly step-and atom-economical benzofulvenation through free amine-directed ortho CÀH bond activation of o-arylanilines. This paper presents a novel, simple, and efficient approach for the synthesis of benzofulvene derivatives from oarylaniline substrates through CÀH bond activation with two diarylacetylenes as an implicit benzofulvene unit. The reactivity of synthesized benzofulvenes toward oxidation was investigated, and they were shown to transform into phenanthridines, oxabenzofulvenes, and fluorescent polycyclics.

Unique dual‐emissive and deep‐blue/green fluorescent multi‐substituted 4‐azapyrenes with bathochromic shift emission, quantum yields up to 0.60 and long excited‐state lifetime were synthesized successfully by annulative π‐extension reactions. This synthesis constitutes a palladium‐catalyzed dehydrogenative annulation of N‐acyl‐2‐aminobiaryls with in situ 1,3‐diynes as a key step, giving substituted phenanthrenes via a rollover C−H bond activation, followed by Bischler‐Napieralski cyclization. Further π‐extension by superacid‐mediated cyclization produced a blue fluorescent naphtho 4‐azapyrene.

A novel and efficient reductive N-alkenylation of iminoquinones with electron-deficient olefins has been successfully developed by Pd­(II)-catalyzed redox-neutral reactions, which provides a synthesis of tertiary (E)-enamines. We further demonstrate that the tertiary enamines can be converted to multifarious N-heterocyclic compounds, indoles, and quinolones in good yields.

We developed palladium-catalyzed oxidative coupling of olefins with N-acyl 2-aminobiaryls through a sequence of ortho C-H bond activation/alkene insertion/reductive elimination. Furthermore, we controlled the selectivity of mono- and bis-alkenylation products with the solvent effect. The developed protocol was promising for a broad substrate scope ranging from activated olefins with a wide variety of functional groups to unactivated olefins.

A palladium-catalyzed C–H functionalization of an external ring of N-acyl 2-aminobiaryl with bicyclo[2.2.1]­hept-2-ene (norbornene) via multiple C–H bond activations was developed. This study is the first report of the formation of bis-norbornene annulated biarylamines isomers (syn-3a′/anti-3a′ = 36:64) from multiple C–H bond functionalizations. Additionally, nondirected C–H bond functionalization at the C-4′ position with alkenes rendered complete C–H functionalization of five C–H bonds that formed a stable hexasubstituted benzene ring.