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. 2025 Jul 28;5(8):4106-4113.
doi: 10.1021/jacsau.5c00759. eCollection 2025 Aug 25.

Catalytic Dioxygen Activation Using a Diketopiperazine and a Manganese Catalyst for Selective C(sp3)-H Oxidation

Kyriaki Gennaiou  1 , Arnau Call  2 , Nikos Siakavaras  2 , Miquel Costas  2 , Alexandros L Zografos  1
Affiliations

Catalytic Dioxygen Activation Using a Diketopiperazine and a Manganese Catalyst for Selective C(sp3)-H Oxidation

Kyriaki Gennaiou et al. JACS Au. .

Abstract

Activating dioxygen for the selective oxidation of alkanes remains a significant challenge in chemical synthesis. A key limitation lies in identifying efficient electron donors that can partially reduce and thus activate dioxygen while remaining stable in the presence of the resulting reactive oxygen species. Additionally, uncontrolled radical pathways often compromise chemoselectivity in reactions where O2 is used as oxidant. In this study, we report a pyrrole-proline diketopiperazine (DKP) catalyst that synergizes with manganese complexes to activate dioxygen for selective C-H oxidation of alkanes. This strategy achieves high chemoselectivity across diverse substrates under aerobic conditions and delivers moderate to good yields, particularly for benzylic and strained cyclic alkanes.

Keywords: C−H functionalization; O2 activation; aerobic oxidation; biomimetic oxidation; green oxidation; nonheme metal-oxo catalysis; organocatalyst-metal synergy; site-selective oxidation.

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Figures

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1. Aerobic Oxidation, under the Lenses of Monooxygenases (A), Prior (B, C) and Current Work (D)
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2. Reaction Profile for Aerobic Oxidations
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3. Reaction Scope of Aerobic CH-Oxidation Reaction in Comparison with Hydrogen Peroxide C–H Oxidation
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