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
Article, Secondary publication, Publisher's Version
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Item Type: | Article |
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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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