Bottom‐Up Synthesis of Acrylic and Styrylic RhII Carboxylate Polymer Beads: Solid‐Supported Analogs of Rh2(OAc)4

We have developed a short and efficient bottom‐up synthesis of acrylic and styrylic polymer beads containing dirhodium(II) tetracarboxylates. The solid supported dirhodium(II) tetracarboxylate catalysts were synthesized in as little as two steps overall from dirhodium tetratrifluoroacetate and comme...

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Bibliographic Details
Published in:European journal of organic chemistry 2018-12, Vol.2018 (44), p.6150-6157
Main Authors: Levchenko, Vladimir, Sundsli, Bård, Øien‐Ødegaard, Sigurd, Tilset, Mats, Hansen, Finn K., Bonge‐Hansen, Tore
Format: Article
Language:English
Subjects:
Analogs
Anchors
Beads
Bottom‐up synthesis
Carbene ligands
Carboxylic acids
Catalysis
Catalysts
Chemical synthesis
Crosslinking
Cyclopropanation
Heterogeneous catalysis
Immobilization
Ligands
Polymers
Recovering
Rhodium
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Summary:We have developed a short and efficient bottom‐up synthesis of acrylic and styrylic polymer beads containing dirhodium(II) tetracarboxylates. The solid supported dirhodium(II) tetracarboxylate catalysts were synthesized in as little as two steps overall from dirhodium tetratrifluoroacetate and commercially available carboxylic acids, making the bottom‐up approach a viable alternative to the post‐modification approach commonly used. The dirhodium(II) tetracarboxylate polymer beads have a convenient size (ca. 100 µm), are easy to handle, and can be considered solid‐supported analogs of Rh2(OAc)4. Beads generated from dirhodium(II) tetracarboxylates with four polymerizable carboxylate ligands displayed the best catalytic performance and compared favorably to Rh2(OAc)4 in benchmarked cyclopropanation reactions. The results imply that the cumbersome synthesis of monomeric dirhodium(II) tetracarboxylates with mixed ligands systems can be avoided and that immobilized dirhodium(II)‐catalysts with a higher degree of crosslinking is a viable option to catalysts linked in an anchor‐like fashion. We demonstrate recovery and recycling, and a potential use of the beads as catalysts in a cyclopropanation reaction towards the insecticide chrysanthemic acid. Polymer beads containing dirhodium(II) tetracarboxylates can be made in only two steps from commercially available starting materials. The beads can be considered immobilized analogs of Rh2(OAc)4 and compare favorably in benchmark cyclopropanation reactions of styrene with ethyl diazoacetate.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.201800953