The Evolution of Fe-catalyzed Nucleophilic Activation of Acceptor-substituted Vinyl- and Arylcyclopropanes

Acceptor-substituted vinyl- (VCP) and arylcyclopropanes (ACP) are reactive substrates for nucleophilic activation using Bu4N[Fe(CO)(3)(NO)] (TBA[Fe]). In this account, the application of this catalytic strategy in traceless allylic substitution, [3+2]-cycloaddition, and Cloke-Wilson rearrangement will be presented. Additional information, derived from detailed spectroscopic and theoretical investigations, is discussed. These results not only lead to a deeper understanding of the reactivity of the catalyst in VCP and ACP activation, but also set the stage for a new type of catalyst activation using photochemical irradiation at 415nm.