C–C bond activation enabled by dyotropic rearrangement of Pd(IV) species

The weak carbon–metal bond combined with the kinetic inertness of carbon–carbon bond renders the metal catalyzed C–C bond activation to be highly challenging. Most of the reported C–C bond activation methodologies involve the strain-releasing cleavage of small rings to compensate the unfavorable kinetic and thermodynamic penalties associated with the C–C bond cleavage. Here we report that the 1,2-positional interchange of vicinal C–C and C–Pd(IV) bonds (dyotropic rearrangement) can be realized in a stereospecific manner under mild conditions, giving access to quaternary carbon-palladium bonds. An enantioselective synthesis of medicinally relevant fluorinated cyclopentanes, featuring this rearrangement as a key step, has been developed. We anticipate that implementing a Pd-based dyotropic rearrangement in reaction design could provide a new dimension in the development of Pd-catalyzed transformations.