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 β-aminoboronates, which are important compounds in drug discovery, being a bioisostere of β-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.
Two-step dearomativef unctionalization 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 wasd emonstrated and provided the corresponding dearomatized products.
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.
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