Open AccessC–C bond activation enabled by dyotropic rearrangement of Pd(iv) species
Author(s) -
Jian Cao,
Hua Wu,
Qian Wang,
Jieping Zhu
Publication year - 2021
Publication title -
nature chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 9.996
H-Index - 232
eISSN - 1755-4349
pISSN - 1755-4330
DOI - 10.1038/s41557-021-00698-y
Subject(s) - chemistry , bond cleavage , vicinal , cyclopentanes , single bond , enantioselective synthesis , cleavage (geology) , ring strain , palladium , metal , stereochemistry , carbon fibers , catalysis , combinatorial chemistry , organic chemistry , molecule , alkyl , geotechnical engineering , fracture (geology) , engineering , materials science , composite number , composite material
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.