Homogeneous–Heterogeneous Hybrid Oxidation Catalysis Based on Multiple Adsorption Enabling Efficient Aerobic Amide Oxygenation
- 1Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Tokyo, Japan, 113-8656
- 2Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, 1-1 Minami Osawa, Hachioji, Tokyo, Japan, 192-0397
- 3Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama, Japan, 332-0012
Abstract
Homogeneous–heterogeneous combined catalysts, such as immobilized homogeneous catalysts and single-atom catalysts (SACs), have been developed to improve catalytic performance and practicality and elucidate catalytic mechanisms. However, achieving new catalytic functions beyond those of the individual components remains challenging. Homogeneous–heterogeneous hybrid catalysis offers a contrasting approach: homogeneous catalysts can coordinate/adsorb onto heterogeneous catalysts, allowing the two components to cooperate and potentially enable new catalytic processes for efficient molecular transformations. Nevertheless, reports of such hybrid catalysis remain limited, particularly for oxidation catalysis. We achieved effective homogeneous–heterogeneous hybrid oxidation catalysis by adsorbing a homogeneous phthalimide N-oxyl (PINO) radical catalyst onto a supported heterogeneous Pd nano-(hydr)oxide catalyst, enabling efficient aerobic α-oxygenation of structurally diverse amides (up to 99% yield; 15 examples). This hybrid oxidation system also accommodated amides that possess α-C–H bonds with high bond dissociation energies and are challenging substrates for previously reported amide α-oxygenation systems, including those involving direct hydrogen atom transfer (HAT) by PINO. Comprehensive characterization, control experiments, kinetic studies, and detailed comparisons with Co-catalyzed systems and Pd SACs support that the hybrid radical species formed on the Pd nano-(hydr)oxide surface through PINO adsorption efficiently facilitate HAT of amides via their coadsorption at nearby Pd sites.
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BibTeX
@misc{wakabayashi2026homogeneousheterogeneous,
title = {{Homogeneous–Heterogeneous Hybrid Oxidation Catalysis Based on Multiple Adsorption Enabling Efficient Aerobic Amide Oxygenation}},
author = {Sora Wakabayashi and Nobuki Hachimura and Daisuke Takei and Soichi Kikkawa and Seiji Yamazoe and Tomohiro Yabe and Kazuya Yamaguchi and Takafumi Yatabe},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010864/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010864/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Homogeneous–Heterogeneous Hybrid Oxidation Catalysis Based on Multiple Adsorption Enabling Efficient Aerobic Amide Oxygenation
AU - Sora Wakabayashi
AU - Nobuki Hachimura
AU - Daisuke Takei
AU - Soichi Kikkawa
AU - Seiji Yamazoe
AU - Tomohiro Yabe
AU - Kazuya Yamaguchi
AU - Takafumi Yatabe
PY - 2026
DA - 2026/10/22
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010864/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010864/v1
AB - Homogeneous–heterogeneous combined catalysts, such as immobilized homogeneous catalysts and single-atom catalysts (SACs), have been developed to improve catalytic performance and practicality and elucidate catalytic mechanisms. However, achieving new catalytic functions beyond those of the individual components remains challenging. Homogeneous–heterogeneous hybrid catalysis offers a contrasting approach: homogeneous catalysts can coordinate/adsorb onto heterogeneous catalysts, allowing the two components to cooperate and potentially enable new catalytic processes for efficient molecular transformations. Nevertheless, reports of such hybrid catalysis remain limited, particularly for oxidation catalysis. We achieved effective homogeneous–heterogeneous hybrid oxidation catalysis by adsorbing a homogeneous phthalimide N-oxyl (PINO) radical catalyst onto a supported heterogeneous Pd nano-(hydr)oxide catalyst, enabling efficient aerobic α-oxygenation of structurally diverse amides (up to 99% yield; 15 examples). This hybrid oxidation system also accommodated amides that possess α-C–H bonds with high bond dissociation energies and are challenging substrates for previously reported amide α-oxygenation systems, including those involving direct hydrogen atom transfer (HAT) by PINO. Comprehensive characterization, control experiments, kinetic studies, and detailed comparisons with Co-catalyzed systems and Pd SACs support that the hybrid radical species formed on the Pd nano-(hydr)oxide surface through PINO adsorption efficiently facilitate HAT of amides via their coadsorption at nearby Pd sites.
ER -