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

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 sulfoxantpho...

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Published in:Green chemistry : an international journal and green chemistry resource : GC 2020-11, Vol.22 (22), p.7974-7982
Main Authors: Terhorst, M., Plass, C., Hinzmann, A., Guntermann, A., Jolmes, T., Rösler, J., Panke, D., Gröger, H., Vogt, D., Vorholt, A. J., Seidensticker, T.
Format: Article
Language:English
Subjects:
Aldehydes
Alkenes
Biocatalysts
Butanol
Catalysts
Condensates
Coordination compounds
Cyanides
Dehydration
Design of experiments
Design optimization
Green chemistry
Hydroxylamine
Intermediates
Nitriles
Regioselectivity
Rhodium
Solvents
Styrene
Substrates
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Summary: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.
ISSN:1463-9262
1463-9270
DOI:10.1039/D0GC03141K