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50 Years of Giese Reaction - a Personal View
Martin Spichty1, Hendrik Zipse2, Salem Majouri3
1Laboratoire d'Innovation Moléculaire et Applications (UMR 7042), Université de Strasbourg|Université de Haute-Alsace|CNRS-IRJBD, 3 bis rue Alfred Werner, Mulhouse, 68057 CEDEX, France.
Angewandte Chemie (International Ed. in English)
|December 12, 2025
Summary
The Giese reaction, a 50-year-old synthetic method, enables 1:1:1-addition products via radical precursors. Biological systems utilize similar strategies, but at protein interfaces, influencing reaction outcomes.
Area of Science:
- Organic Chemistry
- Biochemistry
- Chemical Synthesis
Background:
- The Giese reaction, a synthetic method for C,C-bond formation, was discovered 50 years ago.
- It involves alkyl radical precursors, alkenes, and hydrogen donors in cyclic chain reactions.
- Understanding substituent effects on reactivity and selectivity is crucial for intermolecular radical reactions.
Purpose of the Study:
- To explore the application of Giese reaction principles in biological systems.
- To compare synthetic strategies in laboratory vessels versus biological cells.
- To investigate the influence of interfaces and metallo-cofactors in biological radical reactions.
Main Methods:
- Experimental elucidation of reactivity and selectivity rules for radical reactions.
- Comparative analysis of chemical syntheses in homogeneous solutions and biological interfaces.
- Investigation of metallo-cofactor mediated radical generation via long-distance electron transfer.
Main Results:
- The Giese reaction provides a versatile method for synthesizing 1:1:1-addition products.
- Biological systems employ similar radical strategies, but at protein/water interfaces.
- Thermodynamic interactions at interfaces and metallo-cofactors significantly influence biological radical syntheses.
Conclusions:
- The fundamental rules of radical chemistry apply in both laboratory and biological settings.
- Biological reaction environments, particularly interfaces, introduce thermodynamic control distinct from kinetic control in solution.
- Metallo-cofactors play a key role in initiating radical reactions within cells.
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