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![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Catalysiscubed Reloaded─Cyclopropanations inside Porphyrin-Based Supramolecular M8L6 Aggregates
Theresa Lena Harings1, Bas de Bruin2, Arne Lützen1
1University of Bonn, Gerhard-Domagk-Straße 1, Bonn D-53121, Germany.
Metallosupramolecular cages encapsulate cobalt catalysts, enhancing performance in cyclopropanation reactions. This compartmentalization improves catalyst activity and selectivity for terminal alkenes, demonstrating the benefits of confined catalytic environments.
Area of Science:
- Supramolecular Chemistry
- Organometallic Chemistry
- Catalysis
Background:
- Metallosupramolecular cages offer unique microenvironments for catalyst design.
- Cobalt catalysts with porphyrin ligands are explored for cyclopropanation reactions.
Purpose of the Study:
- To evaluate the performance of cobalt catalysts encapsulated within M8L6 cages for radical cyclopropanation.
- To investigate the impact of encapsulation on catalyst activity, selectivity, and stereochemical outcome.
Main Methods:
- Synthesis of M8L6 metallosupramolecular cages.
- Encapsulation of cobalt-porphyrin catalysts within the cages.
- Evaluation of catalytic activity in radical cyclopropanation of styrene derivatives.
Main Results:
- Encapsulated catalysts showed enhanced performance (TON) compared to free analogues.
- Catalyst performance was sensitive to counterion and solvent choice.
- A shift towards cis-diastereoselectivity was observed with caged catalysts.
- Internal alkenes were unreactive under these conditions, indicating substrate selectivity.
Conclusions:
- Compartmentalization of cobalt catalysts in metallosupramolecular cages significantly benefits catalytic performance.
- The unique microenvironment of the cage influences selectivity and stereochemical outcome.
- Metallosupramolecular cages provide a platform for developing highly selective and active catalysts.
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