Journal
NATURE CHEMISTRY
Volume 13, Issue 7, Pages 671-+Publisher
NATURE PORTFOLIO
DOI: 10.1038/s41557-021-00698-y
Keywords
-
Categories
Funding
- EPFL (Switzerland)
- Swiss National Science Foundation [SNSF 200021-178816/1]
- China Scholarship Council
Ask authors/readers for more resources
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.
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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available