Recent Progress in Hydrogen Atom Transfer-Mediated Photocatalytic C(sp3)—H Bond Oxidation

doi:10.6023/cjoc202409016

Abstract

Oxidation reactions are fundamental and practical processes in synthetic chemistry, and achieving selective and efficient oxidation has been a hot topic in this field. Traditional oxidation methods face several challenges, including poor selectivity and difficulty in controlling reactivity. Selective C—H functionalization, especially the selective transformation of C(sp³)—H bonds, enables precise control over functionalization sites and allows for functionalization at some low-reactivity positions, demonstrating significant advantages in synthetic chemistry. Combining selective C(sp³)—H functionalization with oxidation reactions presents a novel approach for achieving high-selectivity in oxidation processes. Hydrogen atom transfer (HAT) is a commonly used method for transforming C(sp³)—H bonds, typically requiring either photochemical or thermal initiation. This article reviews the progress made in the past five years regarding HAT-mediated photochemical oxidation of C(sp³)—H bonds, briefly introducing the reaction mechanisms and substrate applicability of these new systems, and provides an outlook on the future development of HAT-mediated photochemical C(sp³)—H bond oxidation reactions.

Key words: hydrogen atom transfer, photocatalysis, C(sp³)—H oxidation

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Jiahao Huang, Yahao Huang, Peng Hu. Recent Progress in Hydrogen Atom Transfer-Mediated Photocatalytic C(sp³)—H Bond Oxidation[J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1509-1522.

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Fig. & Tab. 18

Figure 1. Common oxidants

Scheme 1. Photocatalytic hydrogen atom transfer (HAT)-mediated benzylic C(sp3)—H trifluoroacetoxylation

Scheme 2. Photocatalytic 1,5-hydrogen atom transfer (HAT)-mediated remote benzylic C(sp3)—H oxidation

Scheme 3. Photocatalytic HAT-mediated benzylic C(sp3)—H oxidation using CeCl3 as a photocatalyst

Scheme 4. Photocatalytic HAT-mediated benzylic C(sp3)—H oxidation using [NEt4]2[CeCl6] as a photocatalyst

Scheme 5. Selective benzylic C(sp3)—H oxidation of ethylbenzene derivatives under continuous flow conditions catalyzed by anthracene-cerium synergistic catalysis

Scheme 6. Photocatalytic amidation of benzylic C(sp3)—H bonds using iron complex as a photocatalyst

Scheme 7. Photocatalytic selective oxidation of benzylic C(sp3)—H bonds using iron complex as a photocatalyst

Scheme 8. Visible light-mediated oxidation of benzylic C(sp3)—H bonds catalyzed by UO22＋

Scheme 9. DT-catalyzed visible light-mediated oxidation of allylic, benzylic, and unactivated C(sp3)—H bonds

Scheme 10. DT-catalyzed visible light-mediated oxidation of amide nitrogen α-C(sp3)—H bonds

Scheme 11. Photocatalytic HAT-mediated oxidation of benzylic C(sp3)—H bonds using sodium trifluoromethanesulfonate as a photocatalyst

Scheme 12. Photocatalytic HAT-mediated allylic C(sp3)—H oxidation using Rose Bengal as a photocatalyst

Scheme 13. Photocatalytic HAT-mediated allylic C(sp3)—H oxidation using Eosin Y as a photocatalyst

Scheme 14. Photocatalytic HAT-mediated alkoxylation of benzylic C(sp3)—H bonds using Mes-Acr＋ClO4－ as a photocatalyst

Scheme 15. Photocatalytic HAT-mediated oxidation of allylic C(sp3)—H bonds using Mes-Acr＋ClO4－ as a photocatalyst

Scheme 16. Photocatalytic HAT-mediated oxidation of benzylic C(sp3)—H bonds using 6-bromobenzo[d]thiazole as a photocatalyst

Scheme 17. Photocatalytic HAT-mediated oxidation of benzylic C(sp3)—H bonds using carbon tetrabromide as a photocatalyst

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氢原子转移介导的光催化C(sp³)—H键氧化反应进展

Recent Progress in Hydrogen Atom Transfer-Mediated Photocatalytic C(sp³)—H Bond Oxidation

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Fig. & Tab. 18

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氢原子转移介导的光催化C(sp3)—H键氧化反应进展