Highly Efficient Rh‐catalysts Immobilised by π‐π Stacking for the Asymmetric Hydroformylation of Norbornene under Continuous Flow Conditions

Anton Cunillera, Carolina Blanco, Aitor Gual, Jakob Maximilian Marinkovic, Eduardo J. Garcia‐Suarez*, Anders Riisager, Carmen Claver, Aurora Ruiz, Cyril Godard

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

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Abstract

The application of C1‐symmetrical diphosphite ligands containing furanose backbone in the Rh‐catalysed asymmetric hydroformylation of norbornene is described. The catalysts were highly active and produced exclusively exo‐norbornanecarboxaldehyde with enantioselectivities (ee) up to 71 %. Considering these promising results, the ligands were modified with a pyrene moiety to accomplish their immobilisation onto carbon materials. The corresponding Rh complexes bearing the novel pyrene‐tagged ligands were synthesised and immobilised onto multiwalled carbon nanotubes (MWCNT), reduced graphene oxide (rGO) and carbon beads (CBs). The novel catalytic systems were tested in the asymmetric hydroformylation of norbornene providing similar performance in terms of both activity and selectivity compared to the non‐immobilised systems. The recyclability of the new heterogenised catalysts was studied in the target reaction in batch mode. Nevertheless, the recycling was unsuccessful due to catalyst leaching. When used under continuous flow mode, these catalysts revealed robust and provided even higher ee than the corresponding homogeneous systems.
Original languageEnglish
JournalChemCatChem
Volume11
Issue number8
Pages (from-to)2195-2205
Number of pages12
ISSN1867-3880
DOIs
Publication statusPublished - 2019

Keywords

  • Continuous flow
  • Diphosphites
  • Enantioselective hydroformylation
  • π interactions
  • Supported Rh catalysts.

Cite this

Cunillera, Anton ; Blanco, Carolina ; Gual, Aitor ; Marinkovic, Jakob Maximilian ; Garcia‐Suarez, Eduardo J. ; Riisager, Anders ; Claver, Carmen ; Ruiz, Aurora ; Godard, Cyril. / Highly Efficient Rh‐catalysts Immobilised by π‐π Stacking for the Asymmetric Hydroformylation of Norbornene under Continuous Flow Conditions. In: ChemCatChem. 2019 ; Vol. 11, No. 8. pp. 2195-2205.
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title = "Highly Efficient Rh‐catalysts Immobilised by π‐π Stacking for the Asymmetric Hydroformylation of Norbornene under Continuous Flow Conditions",
abstract = "The application of C1‐symmetrical diphosphite ligands containing furanose backbone in the Rh‐catalysed asymmetric hydroformylation of norbornene is described. The catalysts were highly active and produced exclusively exo‐norbornanecarboxaldehyde with enantioselectivities (ee) up to 71 {\%}. Considering these promising results, the ligands were modified with a pyrene moiety to accomplish their immobilisation onto carbon materials. The corresponding Rh complexes bearing the novel pyrene‐tagged ligands were synthesised and immobilised onto multiwalled carbon nanotubes (MWCNT), reduced graphene oxide (rGO) and carbon beads (CBs). The novel catalytic systems were tested in the asymmetric hydroformylation of norbornene providing similar performance in terms of both activity and selectivity compared to the non‐immobilised systems. The recyclability of the new heterogenised catalysts was studied in the target reaction in batch mode. Nevertheless, the recycling was unsuccessful due to catalyst leaching. When used under continuous flow mode, these catalysts revealed robust and provided even higher ee than the corresponding homogeneous systems.",
keywords = "Continuous flow, Diphosphites, Enantioselective hydroformylation, π interactions, Supported Rh catalysts.",
author = "Anton Cunillera and Carolina Blanco and Aitor Gual and Marinkovic, {Jakob Maximilian} and Garcia‐Suarez, {Eduardo J.} and Anders Riisager and Carmen Claver and Aurora Ruiz and Cyril Godard",
year = "2019",
doi = "10.1002/cctc.201900211",
language = "English",
volume = "11",
pages = "2195--2205",
journal = "ChemCatChem",
issn = "1867-3880",
publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",
number = "8",

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Highly Efficient Rh‐catalysts Immobilised by π‐π Stacking for the Asymmetric Hydroformylation of Norbornene under Continuous Flow Conditions. / Cunillera, Anton; Blanco, Carolina; Gual, Aitor; Marinkovic, Jakob Maximilian; Garcia‐Suarez, Eduardo J.; Riisager, Anders; Claver, Carmen; Ruiz, Aurora; Godard, Cyril.

In: ChemCatChem, Vol. 11, No. 8, 2019, p. 2195-2205.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Highly Efficient Rh‐catalysts Immobilised by π‐π Stacking for the Asymmetric Hydroformylation of Norbornene under Continuous Flow Conditions

AU - Cunillera, Anton

AU - Blanco, Carolina

AU - Gual, Aitor

AU - Marinkovic, Jakob Maximilian

AU - Garcia‐Suarez, Eduardo J.

AU - Riisager, Anders

AU - Claver, Carmen

AU - Ruiz, Aurora

AU - Godard, Cyril

PY - 2019

Y1 - 2019

N2 - The application of C1‐symmetrical diphosphite ligands containing furanose backbone in the Rh‐catalysed asymmetric hydroformylation of norbornene is described. The catalysts were highly active and produced exclusively exo‐norbornanecarboxaldehyde with enantioselectivities (ee) up to 71 %. Considering these promising results, the ligands were modified with a pyrene moiety to accomplish their immobilisation onto carbon materials. The corresponding Rh complexes bearing the novel pyrene‐tagged ligands were synthesised and immobilised onto multiwalled carbon nanotubes (MWCNT), reduced graphene oxide (rGO) and carbon beads (CBs). The novel catalytic systems were tested in the asymmetric hydroformylation of norbornene providing similar performance in terms of both activity and selectivity compared to the non‐immobilised systems. The recyclability of the new heterogenised catalysts was studied in the target reaction in batch mode. Nevertheless, the recycling was unsuccessful due to catalyst leaching. When used under continuous flow mode, these catalysts revealed robust and provided even higher ee than the corresponding homogeneous systems.

AB - The application of C1‐symmetrical diphosphite ligands containing furanose backbone in the Rh‐catalysed asymmetric hydroformylation of norbornene is described. The catalysts were highly active and produced exclusively exo‐norbornanecarboxaldehyde with enantioselectivities (ee) up to 71 %. Considering these promising results, the ligands were modified with a pyrene moiety to accomplish their immobilisation onto carbon materials. The corresponding Rh complexes bearing the novel pyrene‐tagged ligands were synthesised and immobilised onto multiwalled carbon nanotubes (MWCNT), reduced graphene oxide (rGO) and carbon beads (CBs). The novel catalytic systems were tested in the asymmetric hydroformylation of norbornene providing similar performance in terms of both activity and selectivity compared to the non‐immobilised systems. The recyclability of the new heterogenised catalysts was studied in the target reaction in batch mode. Nevertheless, the recycling was unsuccessful due to catalyst leaching. When used under continuous flow mode, these catalysts revealed robust and provided even higher ee than the corresponding homogeneous systems.

KW - Continuous flow

KW - Diphosphites

KW - Enantioselective hydroformylation

KW - π interactions

KW - Supported Rh catalysts.

U2 - 10.1002/cctc.201900211

DO - 10.1002/cctc.201900211

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