Molecular Oxygen Beyond Oxidation: Non-Oxidative and Borderline Transformations in Organic Synthesis
- 1Department of Organic and Inorganic Chemistry, Faculty of Science and Technology, University of the Basque Country (EHU), Sarriena auzoa z/g, 48940 Leioa, Spain
Abstract
Dioxygen is vital for life and a key oxidant in biological systems. Its importance, however, extends beyond living processes; it has been harnessed for diverse applications since antiquity. In synthetic chemistry, oxygen-mediated oxidations are fundamental transformations. Nevertheless, molecular oxygen can also facilitate reactions without a net oxidative outcome. Intriguingly, this role, which defies conventional portrayal of oxygen as an oxidizing agent, has occasionally been noted in the literature. In some cases, oxygen mediates or induces reactions in which the oxidation state of the target organic compound remains unchanged, or the overall transformation does not involve the net incorporation of oxygen or the removal of hydrogen (or hydrogen equivalents) from the organic substrate. In these transformations, oxygen facilitates formally redox-neutral reactions or processes in which the combined number of heteroatoms, π bonds, and ring structures in the product does not exceed that in the reactant. This review covers oxygen-mediated or -induced reactions that meet these criteria. By presenting mechanistic insights and experimental investigations, it highlights behavior of dioxygen in these transformations. This analysis broadens our understanding of versatility of oxygen in synthetic chemistry and supports the development of more sustainable chemical processes.
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BibTeX
@article{obieta2026molecular,
title = {{Molecular Oxygen Beyond Oxidation: Non-Oxidative and Borderline Transformations in Organic Synthesis}},
author = {Maria Obieta and Garazi Urgoitia and María Teresa Herrero and Raul SanMartin},
journal = {Catalysts},
year = {2026},
month = oct,
doi = {10.3390/catal16100907},
url = {https://www.mdpi.com/2073-4344/16/10/907},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Molecular Oxygen Beyond Oxidation: Non-Oxidative and Borderline Transformations in Organic Synthesis
AU - Maria Obieta
AU - Garazi Urgoitia
AU - María Teresa Herrero
AU - Raul SanMartin
PY - 2026
DA - 2026/10/14
JO - Catalysts
DO - 10.3390/catal16100907
UR - https://www.mdpi.com/2073-4344/16/10/907
AB - Dioxygen is vital for life and a key oxidant in biological systems. Its importance, however, extends beyond living processes; it has been harnessed for diverse applications since antiquity. In synthetic chemistry, oxygen-mediated oxidations are fundamental transformations. Nevertheless, molecular oxygen can also facilitate reactions without a net oxidative outcome. Intriguingly, this role, which defies conventional portrayal of oxygen as an oxidizing agent, has occasionally been noted in the literature. In some cases, oxygen mediates or induces reactions in which the oxidation state of the target organic compound remains unchanged, or the overall transformation does not involve the net incorporation of oxygen or the removal of hydrogen (or hydrogen equivalents) from the organic substrate. In these transformations, oxygen facilitates formally redox-neutral reactions or processes in which the combined number of heteroatoms, π bonds, and ring structures in the product does not exceed that in the reactant. This review covers oxygen-mediated or -induced reactions that meet these criteria. By presenting mechanistic insights and experimental investigations, it highlights behavior of dioxygen in these transformations. This analysis broadens our understanding of versatility of oxygen in synthetic chemistry and supports the development of more sustainable chemical processes.
SN - 2073-4344
ER -