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Updated: Apr 12, 2026
09:35
Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
Published on: September 18, 2016
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Copper(I)-Catalyzed Cycloaddition of Azides to Multiple Alkynes: A Selectivity Study Using a Calixarene Framework
Alexander Gorbunov1, Dmitry Cheshkov2, Vladimir Kovalev3
1Department of Chemistry, M. V. Lomonosov Moscow State University, Lenin's Hills 1, 119991 Moscow (Russia).
Chemistry (Weinheim an Der Bergstrasse, Germany)
|May 19, 2015
Summary
Copper(I)-catalyzed azide-alkyne cycloaddition on calixarene platforms yielded selective triazole formation. This cascade process is driven by intramolecular copper(I) ion transfer, not autocatalysis or complexation.
Area of Science:
- Organic Chemistry
- Supramolecular Chemistry
- Catalysis
Background:
- Copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) is a key click chemistry reaction.
- Controlling selectivity in CuAAC reactions with multiple alkyne groups is challenging.
- Calixarene platforms offer pre-organized structures for controlled chemical transformations.
Purpose of the Study:
- To investigate the selective formation of triazole derivatives on calixarene platforms.
- To elucidate the mechanism behind the observed selectivity in CuAAC reactions.
- To explore the role of calixarene structure in directing the reaction outcome.
Main Methods:
- Synthesis of calixarene platforms functionalized with multiple propargyl groups.
- Copper(I)-catalyzed azide-alkyne cycloaddition reactions under varying conditions.
- Mechanistic studies including investigation of autocatalysis and copper-triazole complexation.
- Kinetic modeling to understand the cascade process.
Main Results:
- Observed unprecedented selective formation of exhaustively triazolated calixarenes.
- Demonstrated that selectivity is dependent on calixarene structure and reaction conditions.
- Disproved autocatalytic copper activation and copper(I) concentration increase via complexation as selectivity drivers.
- Identified an intramolecular copper(I) ion transfer mechanism in a cascade process.
Conclusions:
- The selectivity in CuAAC on calixarene platforms is governed by a novel intramolecular copper(I) ion transfer mechanism.
- The pre-organized nature of calixarene scaffolds plays a crucial role in achieving high selectivity.
- This study provides new insights into controlling complex chemical reactions on supramolecular architectures.
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