C-C bond activation enabled by dyotropic rearrangement of Pd(iv) species

The weak carbon-metal bond combined with the kinetic inertness of the carbon-carbon bond renders metal-catalysed C-C bond activation to be highly challenging. Most of the reported C-C bond activation methodologies involve strain-releasing cleavage of small rings to compensate for unfavourable kinetic and thermodynamic penalties associated with 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 tool in the development of Pd-catalysed transformations.

Automated summary

The study presents a method for the stereospecific interchange of vicinal C-C and C-Pd(iv) bonds under mild conditions, leading to the formation of quaternary carbon-palladium bonds. The enantioselective synthesis of fluorinated cyclopentanes utilizing this rearrangement has been developed, showcasing the potential of implementing a Pd-based dyotropic rearrangement in catalytic transformations.