Intermolecular annulation reactions of 1-aryl-2-naphthols with internal alkynes proceed efficiently in the presence of a Ru catalyst and a Cu oxidant to generate spirocyclic compounds by sequential cleavage of the C(sp(2))-H bond, migratory insertion of the alkyne, and dearomatization of the naphthyl ring. Various spirocyclic molecules bearing an all-carbon quaternary stereocenter could be obtained by this novel method with good yields and excellent regioselectivity, and the current process tolerates a variety of synthetically important functional groups.

The regiospecific [2 + 2] cycloaddition of cyclic isoimidium salts with ynamides is described. This effort led to the development of the first successful example of a catalyst-free, thermally driven Ficini [2 + 2] cycloaddition process of ynamides with α,β-unsaturated carbonyl compounds, giving the stable cyclobutenamides in excellent yields (up to 99%).

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. Preliminary results with commercially available chiral ligands indicate that enantioselective variants are feasible for both cyclization processes.