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

• Published in: Nature chemistry Vol. 13; no. 7; pp. 671 - 676
• Main Authors: Cao, Jian, Wu, Hua, Wang, Qian, Zhu, Jieping
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01.07.2021; NATURE PORTFOLIO; Nature Publishing Group
• Subjects: 639/638/403/933; 639/638/549/933; 639/638/77/883; 639/638/77/888; Analytical Chemistry; Biochemistry; Bonding; Carbon; Chemistry; Chemistry and Materials Science; Chemistry, Multidisciplinary; Chemistry/Food Science; Cleavage; Covalent bonds; Enantiomers; Fluorination; Inorganic Chemistry; Organic Chemistry; Palladium; Physical Chemistry; Physical Sciences; Science & Technology; Synthesis; SYMMETRY CONTROLLED REACTIONS; PALLADIUM; ALKENES; AMINATION; PD(III); CONSTRUCTION; COMPLEXES; CLEAVAGE; REDUCTIVE ELIMINATION
• ISSN: 1755-4330; 1755-4349
• DOI: 10.1038/s41557-021-00698-y

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. Many C–C bond activation methods involve strain-releasing cleavage of small rings to compensate for unfavourable kinetics and thermodynamics. Now, the 1,2-positional interchange of vicinal C–C and C–Pd bonds has been reported, giving access to quaternary carbon–palladium bonds. This dyotropic rearrangement has been used for the enantioselective synthesis of functionalized fluorinated cyclopentanes.