Palladium-Catalyzed C-H Arylation/Arene Dearomatization Domino Reaction: Expeditious Access to Spiro[4,5]fluorenes.

A palladium-catalyzed C-H arylation/arene dearomatization of α-aryl-β-naphthol with -dihalobenzenes was realized in a redox-neutral manner. This bimolecular domino reaction was initiated by an in situ-formed Pd(II) species generated from the dihalobenzene, followed by phenolic-group-directed C-H activation, biaryl cross-coupling, and naphthol dearomatization, thus rendering the rapid assembly of a class of spiro[4,5]fluorenes in high yields with good chemoselectivity. Remarkably, malononitrile-derived spirofluorene was found to exhibit mechanoresponsive luminescence, which can be applied to optical memory devices.

Palladium-Catalyzed Alkenyl C-H Activation/Diamination toward Tetrahydrocarbazole and Analogs Using Hydroxylamines as Single-Nitrogen Sources.

A palladium-catalyzed alkenyl C-H activation/diamination reaction of cycloalkenyl bromoarenes with hydroxylamines is described. A wide range of tetrahydrocarbazoles and analogs has been prepared using fine-tuning bifunctional secondary hydroxylamines as the single-nitrogen sources. Mechanistic investigations suggest that the selective alkenyl C-H activation/diamination cascade process should build the N-heterocycles.

A chemo- and regioselective Pd(0)-catalyzed three-component spiroannulation.

A chemo- and regioselective Pd(0)-catalyzed spiroannulation has been successfully developed. The key feature of this method is the use of readily available 1,2-dihaloarenes, alkynes and 2-naphthols for the rapid assembly of spirocarbocyclic molecules. Mechanistic studies revealed that this domino reaction proceeded through a cascade of oxidative addition to Pd(0), alkyne migratory insertion, and 2-naphthol-facilitated dearomatizing [4+1] spiroannulation.

Palladium(0)-Catalyzed Intermolecular Carbocyclization of (1,n)-Diynes and Bromophenols: An Efficient Route to Tricyclic Scaffolds.

A novel palladium(0)-catalyzed dearomative cyclization reaction of bromophenols with (1,n)-diynes has been developed for building two new types of tricyclic architectures containing a quaternary carbon center. This method employs inexpensive bromophenols, and easily accessible tethered diynes. It exhibits a broad substrate scope and tolerates various functional groups.