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![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
C-C bond activation enabled by dyotropic rearrangement of Pd(IV) species
Jian Cao1,2, Hua Wu1, Qian Wang1
1Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, Lausanne, Switzerland.
Abstract:
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.
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