C–H Functionalization via Single Atom Metathesis of C–H and C–X Bonds
Year: 2025
Type: article
Abstract: Metathesis and reversible catalytic reactions are fundamentally intriguing and powerful tools in modern synthetic chemistry. While most reversible catalytic reactions are predicated on breaking and forming reactive functional groups, the ability to leverage the C-H bond as a functional group in metathesis reactions has proved to be exceptionally challenging. Here, we develop a C-H/C-X metathesis reaction through a radical swapping protocol where hydrogen and halogen are traded between molecules via reversible hydrogen atom transfer (HAT) and halogen atom transfer (XAT) that allows for mild C-H halogenation. The reversibility of this process allows for the selective dehalogenation of polyhalogenated products to form monohalogenated products. Leveraging the reversibility of this process, halogenated organic pollutants can also serve as halogen sources for C-H halogenation. In a broader context, this work establishes that incorporating reversible metathesis logic in C-H bond functionalization can provide complementary advantages in synthetic strategies.
DOI: 10.1021/jacs.5c04754
Institutions: ETH Zurich, Laboratory of Organic Chemistry
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Awards: Merging reversible catalysis with radical reactions for sustainable organic synthesis, Diffractometer with rotating anode, G4776872453, Shuttle Catalysis for Reversible Molecular Construction, Merging functional group metathesis with C–H bond functionalization for molecular editing and feedstock valorization
OpenAlex ID: W4411418335