Palladium-Catalyzed Transformations of Fluorinated Cyclopropanes
Summary
Fluorinated cyclopropanes, particularly the gem-difluoro variants, have emerged as highly strained and versatile building blocks in modern synthesis. The introduction of a palladium catalyst enables selective activation of C–C and C–F bonds within these three-membered rings, facilitating ring-opening and subsequent bond‐forming events under mild conditions. Key transformations include defluorinative functionalisation to yield monofluoroalkenes, allylic substitution pathways to access fluoroallylic scaffolds and hydroxylation processes delivering fluorinated alcohols. Ligand design—often employing N-heterocyclic carbenes—governs chemo-, regio- and stereoselectivity by modulating the balance between inner-sphere pathways, in which the substrate directly binds to palladium before bond formation, and outer-sphere pathways that proceed via metal-associated intermediates without direct substrate coordination. Recent advances have also demonstrated the use of carbon dioxide as an activator in palladium catalysis, pointing towards more sustainable approaches. Collectively, these methods offer access to complex, fluorine-substituted motifs of importance in pharmaceuticals, agrochemicals and materials science.
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Palladium-Catalyzed Transformations of Fluorinated Cyclopropanes publication trend
The graph below shows the total number of articles in palladium-catalyzed transformations of fluorinated cyclopropanes across all publications each year (not limited to Nature Index journals).
Technical terms
gem-Difluorocyclopropane: A three-membered carbocycle bearing two fluorine atoms on the same carbon atom, characterised by high ring strain and unique reactivity.
Oxidative addition: A step in which palladium(0) inserts into a σ-bond of a substrate, forming a palladium(II) complex and increasing the metal’s oxidation state.
Reductive elimination: The reverse of oxidative addition, wherein two ligands on palladium(II) combine to form a new bond, regenerating palladium(0).
N-Heterocyclic carbene (NHC): A neutral ligand featuring a divalent carbon atom with two non-adjacent nitrogen atoms, stabilising palladium centres and tuning selectivity.
Inner-sphere mechanism: A reaction pathway in which the substrate coordinates directly to the metal centre before bond-forming or bond-breaking events occur.
Defluorinative functionalisation: A transformation in which a C–F bond is selectively cleaved and replaced by a new C–X bond, often through transition-metal catalysis.
References
- Ligand-controlled regioselective and chemodivergent defluorinative functionalization of gem -difluorocyclopropanes with simple ketones. Chemical Science (2021).
- Pd-catalyzed access to mono- and di-fluoroallylic amines from primary anilines. Chemical Communications (2023).
- CO 2 and palladium enabled highly chemoselective hydroxylation of gem -difluorocyclopropanes. Organic Chemistry Frontiers (2024).
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