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Dirhodium complex immobilization on modified cellulose for highly selective heterogeneous cyclopropanation reactions

Rösler, Lorenz ; Höfler, Mark V. ; Breitzke, Hergen ; Wissel, Till ; Herr, Kevin ; Heise, Henrike ; Gutmann, Torsten ; Buntkowsky, Gerd (2023)
Dirhodium complex immobilization on modified cellulose for highly selective heterogeneous cyclopropanation reactions.
In: Cellulose, 2022, 29 (11)
doi: 10.26083/tuprints-00024225
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Item Type: Article
Type of entry: Secondary publication
Title: Dirhodium complex immobilization on modified cellulose for highly selective heterogeneous cyclopropanation reactions
Language: English
Date: 11 July 2023
Place of Publication: Darmstadt
Year of primary publication: 2022
Publisher: Springer Nature
Journal or Publication Title: Cellulose
Volume of the journal: 29
Issue Number: 11
DOI: 10.26083/tuprints-00024225
Corresponding Links:
Origin: Secondary publication service
Abstract:

A novel, efficient approach for the functionalization of microcrystalline cellulose (MCC) is presented. The as-obtained material allows the immobilization of chiral dirhodium catalysts preserving their enantioselectivity in asymmetric cyclopropanation reactions. As model, microcrystalline cellulose is modified with a polyethylene glycol derived linker, and Rh₂(S-DOSP)₄ is grafted on the material to produce a heterogeneous catalyst. SEM images at different stages of the immobilization show an unchanging uniform morphology, providing constantly good separation characteristics. The modification of the cellulose material with the polyethylene derived linker and the immobilization process are monitored using DNP enhanced ¹H → ¹³C CP MAS NMR, quantitative ¹⁹F MAS NMR, TGA and ICP-OES analysis, confirming the success of the immobilization as well as the stability of bonds between the used linker molecule and the cellulose material. Finally, the evaluation of the produced catalyst is demonstrated in the asymmetric cyclopropanation reaction between styrene and methyl(E)-2-diazo-4-phenylbut-3-enoate showing excellent enantioselectivity with an ee of nearly 90% over a wide temperature range as well as good recyclability characteristics in four consecutive catalysis cycles.

Uncontrolled Keywords: Immobilization, Asymmetric cyclopropanation, Dirhodium, NMR spectroscopy, Dynamic nuclear polarization
Status: Publisher's Version
URN: urn:nbn:de:tuda-tuprints-242258
Classification DDC: 500 Science and mathematics > 530 Physics
500 Science and mathematics > 540 Chemistry
Divisions: 07 Department of Chemistry > Eduard Zintl-Institut > Physical Chemistry
Date Deposited: 11 Jul 2023 11:45
Last Modified: 04 Oct 2023 13:42
URI: https://tuprints.ulb.tu-darmstadt.de/id/eprint/24225
PPN: 512013012
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