The enantioselective intermolecular gold(I)-catalyzed [2+2] cycloaddition of terminal alkynes and alkenes has been achieved using non-C₂-chiral Josiphos digold(I) complexes as catalysts, by the formation of the monocationic complex. This new approach has been applied to the enantioselective total synthesis of rumphellaone A.

The alkynylation of naphthols takes place with total regiocontrol at the peri position of the hydroxyl group in the presence of [RuCl₂(p-cymene)]₂ as the catalyst. This reaction features high functional group tolerance. The related ortho-alkynylation of benzoic acids proceeds under similar conditions and also shows wide functional group tolerance. Both reactions proceed through metalation, insertion of the alkyne, and bromide elimination.

The first π-coordination-catalyzed nucleophilic fluorination of unactivated aryl halides has been demonstrated. Chlorobenzene reacts with alkali metal fluorides (CsF, KF) in the presence of a Cp*Ru catalyst at 120–180 °C to give fluorobenzene.