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Updated: Jun 22, 2026

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
How does electrostatic activation control iminium-catalyzed cyclopropanations?
Sami Lakhdar1, Roland Appel, Herbert Mayr
1Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany.
Ordinary alpha,beta-unsaturated iminium ions react with sulfur ylides, contrary to prior beliefs. Strong electrostatic interactions significantly accelerate these reactions and ensure high stereoselectivity.
Area of Science:
- Organic Chemistry
- Reaction Mechanisms
- Stereochemistry
Background:
- Previous studies suggested alpha,beta-unsaturated iminium ions do not react with sulfur ylides.
- Understanding the reactivity of iminium ions is crucial in organic synthesis.
Purpose of the Study:
- To investigate the reaction between ordinary alpha,beta-unsaturated iminium ions and sulfur ylides.
- To elucidate the role of electrostatic interactions in this reaction.
- To determine the factors influencing stereoselectivity.
Main Methods:
- Computational chemistry to model reaction pathways.
- Experimental verification of predicted reactivity.
- Analysis of transition states to understand electrostatic contributions.
Main Results:
- Confirmed that ordinary alpha,beta-unsaturated iminium ions do react with sulfur ylides.
- Identified significant acceleration of reactions ( > 10^5 -fold) due to electrostatic interactions.
- Demonstrated that these electrostatic forces are key to achieving high stereoselectivity.
Conclusions:
- The reactivity of iminium ions with sulfur ylides is established.
- Electrostatic interactions play a dominant role in accelerating these reactions and controlling stereochemical outcomes.
- This finding opens new avenues for synthetic applications.
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