One-pot synthesis of aldoximes from alkenes via Rh-catalysed hydroformylation in an aqueous solvent system

Terhorst M, Plass C, Hinzmann A, Guntermann A, Jolmes T, Roesler J, Panke D, Gröger H, Vogt D, Vorholt AJ, Seidensticker T (2020)
Green Chemistry 22(22): 7974-7982.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
Download
Es wurden keine Dateien hochgeladen. Nur Publikationsnachweis!
Autor*in
Terhorst, M.; Plass, CarmenUniBi; Hinzmann, AlessaUniBi ; Guntermann, AlinaUniBi; Jolmes, T.; Roesler, J.; Panke, D.; Gröger, HaraldUniBi; Vogt, D.; Vorholt, A. J.; Seidensticker, T.
Abstract / Bemerkung
Aldoxime synthesis directly starting from alkenes was successfully achieved through the combination of hydroformylation and subsequent condensation of the aldehyde intermediate with aqueous hydroxylamine in a one-pot process. The metal complex Rh(acac)(CO)(2) and the water-soluble ligand sulfoxantphos were used as the catalyst system, providing high regioselectivities in the initial hydroformylation. A mixture of water and 1-butanol was used as an environmentally benign solvent system, ensuring sufficient contact of the aqueous catalyst phase and the organic substrate phase. The reaction conditions were systematically optimised by Design of Experiments (DoE) using 1-octene as a model substrate. A yield of 85% of the desired linear, terminal aldoxime ((E/Z)-nonanal oxime) at 95% regioselectivity was achieved. Other terminal alkenes were also converted successfully under the optimised conditions to the corresponding linear aldoximes, including renewable substrates. Differences of the reaction rate have been investigated by recording the gas consumption, whereby turnover frequencies (TOFs) >2000 h(-1) were observed for 4-vinylcyclohexene and styrene, respectively. The high potential of aldoximes as platform intermediates was shown by their subsequent transformation into the corresponding linear nitriles using aldoxime dehydratases as biocatalysts. The overall reaction sequence thus allows for a straightforward synthesis of linear nitriles from alkenes with water being the only by-product, which formally represents an anti-Markovnikov hydrocyanation of readily available 1-alkenes.
Erscheinungsjahr
2020
Zeitschriftentitel
Green Chemistry
Band
22
Ausgabe
22
Seite(n)
7974-7982
ISSN
1463-9262
eISSN
1463-9270
Page URI
https://pub.uni-bielefeld.de/record/2949195

Zitieren

Terhorst M, Plass C, Hinzmann A, et al. One-pot synthesis of aldoximes from alkenes via Rh-catalysed hydroformylation in an aqueous solvent system. Green Chemistry. 2020;22(22):7974-7982.
Terhorst, M., Plass, C., Hinzmann, A., Guntermann, A., Jolmes, T., Roesler, J., Panke, D., et al. (2020). One-pot synthesis of aldoximes from alkenes via Rh-catalysed hydroformylation in an aqueous solvent system. Green Chemistry, 22(22), 7974-7982. doi:10.1039/d0gc03141k
Terhorst, M., Plass, C., Hinzmann, A., Guntermann, A., Jolmes, T., Roesler, J., Panke, D., Gröger, H., Vogt, D., Vorholt, A. J., et al. (2020). One-pot synthesis of aldoximes from alkenes via Rh-catalysed hydroformylation in an aqueous solvent system. Green Chemistry 22, 7974-7982.
Terhorst, M., et al., 2020. One-pot synthesis of aldoximes from alkenes via Rh-catalysed hydroformylation in an aqueous solvent system. Green Chemistry, 22(22), p 7974-7982.
M. Terhorst, et al., “One-pot synthesis of aldoximes from alkenes via Rh-catalysed hydroformylation in an aqueous solvent system”, Green Chemistry, vol. 22, 2020, pp. 7974-7982.
Terhorst, M., Plass, C., Hinzmann, A., Guntermann, A., Jolmes, T., Roesler, J., Panke, D., Gröger, H., Vogt, D., Vorholt, A.J., Seidensticker, T.: One-pot synthesis of aldoximes from alkenes via Rh-catalysed hydroformylation in an aqueous solvent system. Green Chemistry. 22, 7974-7982 (2020).
Terhorst, M., Plass, Carmen, Hinzmann, Alessa, Guntermann, Alina, Jolmes, T., Roesler, J., Panke, D., Gröger, Harald, Vogt, D., Vorholt, A. J., and Seidensticker, T. “One-pot synthesis of aldoximes from alkenes via Rh-catalysed hydroformylation in an aqueous solvent system”. Green Chemistry 22.22 (2020): 7974-7982.

Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®

Suchen in

Google Scholar