Benzannulation of phthalic anhydrides with alkynes to polyfunctionalized naphthalenes and phenanthrenes was confirmed to be straightforward using a palladium catalytic system. Sequential liberation of CO2 and CO occurred via oxidative decomposition of anhydride. In the case of 1,8-naphthalenedicarboxylic anhydrides, both aryls were encompassed in the annulation reaction to afford acenaphthylenes.

An atom-economical phosphane-free palladium-catalyzed direct C-2 arylation of unactivated free NH-pyrroles is devised. This method provides a straightforward route to a wide variety of substituted 2-aryl-1H-pyrroles from readily accessible starting materials. Iodoarenes bearing electron-withdrawing and electron-donating substituents are tolerated under the presented reaction conditions. The scope of the reaction is also expanded to N-aryl and -alkylpyrroles albeit in lower yields.

A copper-catalyzed nucleophilic displacement of α-triflyloxy nitriles and esters with silicon nucleophiles allows for the stereospecific generation of highly enantioenriched α-silylated carboxyl compounds. The enantioselective synthesis of α-silylated nitriles is unprecedented. The catalytic system exhibits good functional group tolerance. The stereochemical course of the substitution is shown to proceed with inversion of the configuration. The new reaction is an addition to the still limited number of methods for catalytic C(sp)-Si cross-coupling.

An efficient regioselective synthesis of 2-acylpyrroles via palladium-catalyzed addition of pyrroles with benzonitriles and subsequent hydrolysis is developed. The direct acylation reaction of protected as well as (NH)-free pyrroles proceeded smoothly to afford 2-acylpyrrole scaffolds of high biological interest.

A method for converting geminal dibromides into 1,1-disilylated alkanes is reported. The reaction is promoted by a copper(I) catalyst generated in situ from CuBr·SMe as a precatalyst and 4,4'-di- tert-butyl-2,2'-bipyridine (dtbpy) as a ligand. A Si-B reagent is used as the silicon pronucleophile. It is shown that the two C(sp)-Si bond-forming events differ in mechanism, with the first being ionic and the second being radical.