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Updated: Apr 8, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Progress in intermolecular radical umpolung addition to alkenes
Yeming Wang1,2, Chaoqun Zhang1,2, Jian-Quan Liu3
1Institute of Chemical and Industrial Bioengineering, Jilin Engineering Normal University, Changchun, Jilin, 130052, China. wangyeming2019@163.com.
This review highlights the integration of umpolung (polarity reversal) strategies with radical chemistry for novel organic synthesis. These methods enable efficient C-C bond formation under mild conditions, expanding synthetic possibilities.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
- Radical Chemistry
Background:
- Conventional organic synthesis faces limitations due to polarity, often requiring harsh conditions and multiple steps.
- Umpolung strategies reverse polarity for unconventional bond formations.
- Radical chemistry offers mild conditions for efficient carbon-carbon bond construction.
Purpose of the Study:
- To review recent advances in intermolecular umpolung radical addition to alkenes.
- To summarize key aspects of radical generation, alkene addition, and functionalization.
- To provide mechanistic insights for accessing diverse molecular architectures.
Main Methods:
- Focus on intermolecular reactions involving α-carbonyl, α-sulfonyl, and acyl radicals.
- Discussion of radical generation techniques.
- Analysis of alkene addition mechanisms and subsequent functionalization pathways.
Main Results:
- Demonstration of umpolung radical additions to alkenes as a versatile synthetic paradigm.
- Highlighting efficient methods for C-C bond formation under mild conditions.
- Showcasing access to architecturally diverse molecules.
Conclusions:
- The integration of umpolung and radical chemistry significantly expands the synthetic toolbox.
- These methods provide efficient routes to complex molecules.
- Mechanistic understanding is key to further development in this field.
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