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

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.

SUBMITTER: Cao J

PROVIDER: S-EPMC7611116 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature

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

Cao Jian J Wu Hua H Wang Qian Q Zhu Jieping J

Nature chemistry 20210524 7

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 ste ...[more]

PMID: 34031566

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