Radical Functionalization of Vinyl Cations
Summary
Vinyl cations represent a class of highly reactive intermediates in which the positive charge is delocalised across an unsaturated carbon–carbon framework. Historically, their fleeting existence has limited direct exploitation in synthesis. In recent years, however, innovative strategies have emerged that couple radical reactivity with cationic intermediates, enabling the selective installation of diverse functional groups onto vinyl cations. Photoredox and transition-metal catalysts can generate alkyl or heteroatom radicals that intercept alkenes or pre-formed vinyl cations, sometimes via a radical polar crossover step that converts a radical into a cation. These protocols have unlocked access to tetrasubstituted alkenes, oxyalkylated products and heterocycle precursors under mild conditions. Mechanistic studies have delineated pathways for radical addition, oxidation to vinyl cations and subsequent nucleophilic capture, providing a unified framework for designing new transformations. The expanding repertoire of radical-driven vinyl cation functionalisations promises broad applications in the synthesis of pharmaceuticals, agrochemicals and materials.
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Radical Functionalization of Vinyl Cations publication trend
The graph below shows the total number of articles in radical functionalization of vinyl cations across all publications each year (not limited to Nature Index journals).
Technical terms
Vinyl cation: A positively charged intermediate located on an alkene carbon, characterised by its high reactivity and utility in bond-forming reactions.
Radical functionalisation: The incorporation of functional groups into substrates through species bearing unpaired electrons, enabling transformations under mild and selective conditions.
Radical polar crossover: A mechanistic sequence in which radical intermediates are oxidised or reduced to form ionic species—most commonly carbocations—thereby merging radical and ionic chemistries.
References
- α‑Vinylation of Ester Equivalents via Main Group Catalysis for the Construction of Quaternary Centers. Organic Letters (2023).
- Interaction of Vinyl-Type Carbocations, C3H5+ and C4H7+ with Molecules of Water, Alcohols, and Acetone. Molecules (2023).
- Manganese-Mediated Coupling Reaction of Vinylarenes and Aliphatic Alcohols. Scientific Reports (2015).
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