Reversal of regioselectivity in reactions of donor– acceptor cyclopropanes with electrophilic olefins

Reactivity of donor–acceptor cyclopropanes towards nucleophiles and electrophiles is determined by the specific philicity of the carbon atoms originating from the strong polarization of the central C–C bond. Herein, we report that vitamin B12 catalysis enables the transformation of an initially electrophilic center into a nucleophilic radical that reacts with SOMOphiles. This radical-based strategy reverses the standard regioselectivity and thus complements the classical approaches.For additional details, consult the ODT file. ZIP archive contains raw data from Bruker BioSpin GmbH hardware, standard metadata are contained within the archive.