Electrophilic Trapping of Semibenzenes.

In this work, we demonstrate how allylative dearomatization of benzyl chlorides can provide direct access to a variety of semibenzenes. These scaffolds behave as highly reactive nucleophiles in the presence of carbocations. In addition, semibenzenes are susceptible to intramolecular rearrangements rendering a broad scope of functionalized arenes. An analysis of this new reactivity is reported, as well as the rationale behind the observed intramolecular reorganizations.

Copper-Catalyzed Ring-Opening Reactions of Alkyl Aziridines with B2pin2: Experimental and Computational Studies.

The possibility to form new C-B bonds with aziridines using diboron derivatives continues to be a particularly challenging field in view of the direct preparation of functionalized ß-aminoboronates, which are important compounds in drug discovery, being a bioisostere of ß-aminoacids. We now report experimental and computational data that allows the individuation of the structural requisites and of reaction conditions necessary to open alkyl aziridines using bis(pinacolate)diboron (B2pin2) in a regioselective nucleophilic addition reaction under copper catalysis.

Pd-catalyzed allylative dearomatisation using Grignard reagents.

Pd-catalyzed allylative dearomatisation of naphthyl halides is shown to be feasible by employing Grignard reagents. The high reactivity of the nucleophile allows for fast reactions and low catalyst loading, while a plethora of successfully substituted compounds illustrate the broad scope. Five membered heteroaromatic compounds are also demonstrated to be reactive under similar conditions.

Lewis Acid Promoted Dearomatization of Naphthols.

Two-step dearomative functionalization of naphthols promoted by Lewis acids and copper(I) catalysis was developed. Initially, Lewis acid complexation inverted the electronic properties of the ring and established an equilibrium with the dearomatized counterpart. Subsequent trapping of the dearomatized intermediate with organometallics as well as organophosphines was demonstrated and provided the corresponding dearomatized products.