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Peer-reviewedCC BY 4.0Chemistry (Weinheim an Der Bergstrasse, Germany)

Oxidation of Allylic Alcohols by Manganese Oxides: Elucidating the Influences of MnOx Structure and Mn Oxidation State on Reactivity

  • Erdogan Kasisari1
  • Leandra Meyer1
  • S. Esmael Balaghi1,2,3
  • Harald Scherer1
  • Patrick Elsässer1,2,3,4
  • Anna Fischer1,2,3,4
  • Philipp Kurz1,2
4 affiliations
  1. 1Institut Für Anorganische und Analytische Chemie Albert‐Ludwigs‐Universität Freiburg Freiburg Germany
  2. 2Freiburger Materialforschungszentrum (FMF) Albert‐Ludwigs‐Universität Freiburg Freiburg Germany
  3. 3Freiburg Center for Interactive Materials and Bioinspired Technologies (FIT) Freiburg Germany
  4. 4Cluster of Excellence Living, Adaptive, and Energy‐autonomous Materials Systems (livMatS) Freiburg Germany
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Abstract

Manganese oxides (MnOx) with manganese in oxidation states between +III and +IV are well established in organic synthesis as oxidizing agents for allylic alcohols. In this study, four different MnIII/IVOx were synthesized according to established procedures and—together with commercial “activated MnO2” – investigated in detail concerning their reactivity in the heterogeneous oxidation of the allylic alcohol trans‐pent‐2‐en‐1‐ol. We found that all manganese oxides were able to oxidize trans‐pent‐2‐en‐1‐ol to the corresponding aldehyde with excellent selectivities. However, reaction rates differed greatly depending on the oxides’ structures, morphologies, chemical compositions and average Mn oxidation states. Amorphous manganese oxides with layered structures (birnessite‐type) proved to be especially efficient oxidizing agents and the incorporation of Ca2+ further increased reactivity. Post‐reaction analyses by X‐ray diffraction and X‐ray spectroscopy indicated that most MnOx materials largely retained their structures and Mn oxidation states, whereas Ca‐birnessite showed clear reaction‐induced structural changes and moderate Mn reduction. Very similar results were obtained for the oxidation of the related substrate cinnamyl alcohol. Overall, it can be concluded that the best oxidation agents for this “classic” of organic synthesis are much more complex materials than simply “MnO2” and that the right choice of MnOx is crucial for high product conversions.

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Cite

BibTeXRIS
BibTeX
@article{kasisari2026oxidation,
  title = {{Oxidation of Allylic Alcohols by Manganese Oxides: Elucidating the Influences of MnOx Structure and Mn Oxidation State on Reactivity}},
  author = {Erdogan Kasisari and Leandra Meyer and S. Esmael Balaghi and Harald Scherer and Patrick Elsässer and Anna Fischer and Philipp Kurz},
  journal = {Chemistry (Weinheim an Der Bergstrasse, Germany)},
  year = {2026},
  month = jul,
  doi = {10.1002/chem.71376},
  url = {https://doi.org/10.1002/chem.71376},
  note = {CC BY 4.0},
}
RIS
TY  - JOUR
TI  - Oxidation of Allylic Alcohols by Manganese Oxides: Elucidating the Influences of MnOx Structure and Mn Oxidation State on Reactivity
AU  - Erdogan Kasisari
AU  - Leandra Meyer
AU  - S. Esmael Balaghi
AU  - Harald Scherer
AU  - Patrick Elsässer
AU  - Anna Fischer
AU  - Philipp Kurz
PY  - 2026
DA  - 2026/07/20
JO  - Chemistry (Weinheim an Der Bergstrasse, Germany)
DO  - 10.1002/chem.71376
UR  - https://doi.org/10.1002/chem.71376
AB  - Manganese oxides (MnOx) with manganese in oxidation states between +III and +IV are well established in organic synthesis as oxidizing agents for allylic alcohols. In this study, four different MnIII/IVOx were synthesized according to established procedures and—together with commercial “activated MnO2” – investigated in detail concerning their reactivity in the heterogeneous oxidation of the allylic alcohol trans‐pent‐2‐en‐1‐ol. We found that all manganese oxides were able to oxidize trans‐pent‐2‐en‐1‐ol to the corresponding aldehyde with excellent selectivities. However, reaction rates differed greatly depending on the oxides’ structures, morphologies, chemical compositions and average Mn oxidation states. Amorphous manganese oxides with layered structures (birnessite‐type) proved to be especially efficient oxidizing agents and the incorporation of Ca2+ further increased reactivity. Post‐reaction analyses by X‐ray diffraction and X‐ray spectroscopy indicated that most MnOx materials largely retained their structures and Mn oxidation states, whereas Ca‐birnessite showed clear reaction‐induced structural changes and moderate Mn reduction. Very similar results were obtained for the oxidation of the related substrate cinnamyl alcohol. Overall, it can be concluded that the best oxidation agents for this “classic” of organic synthesis are much more complex materials than simply “MnO2” and that the right choice of MnOx is crucial for high product conversions.
SN  - 0947-6539
SN  - 1521-3765
ER  -