Benzylic Hydroperoxidation via Visible-Light-Induced Csp<sup>3</sup>–H Activation

Inoa, Joan; Patel, Mansi; Dominici, Grecia; Eldabagh, Reem; Patel, Anjali; Lee, John; Xing, Yalan

doi:10.1021/acs.joc.0c00385

Cited by 30 publications

(20 citation statements)

References 42 publications

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“…In 2020, Xing and co-workers discovered a mild and efficient method of obtaining a wide array of benzylic hydroperoxides with the use of neutral eosin Y as a direct HAT photocatalyst in the presence of blue LED light and molecular oxygen (Scheme 5). 24 Peroxides, including hydro-and endo-peroxides, are present in many naturally occurring compounds and are known to possess antimalarial, antibacterial, cytotoxic, as well as other biological activities. 25 Primary, secondary, and tertiary hydroperoxides as well as silyl, benzyl, and acyl peroxides were successfully prepared with good yields and excellent functional group compatibility in this study.…”

Section: Scheme 4 Silane Chlorination Catalyzed By Neutral Eosin Ymentioning

confidence: 99%

Synthetic Applications and Computational Perspectives on Eosin Y Induced Direct HAT Process

Inoa¹,

Dominici²,

Eldabagh³

et al. 2021

Synthesis

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In recent years, advancements in photocatalysis have allowed for a plethora of chemical transformations under milder conditions. Many of these photochemical reactions utilize hydrogen atom transfer processes to obtain desired products. Hydrogen atom transfer processes can follow one of two unique pathways: the first, a direct path and the second, an indirect path. In this paper, we highlight the ability of Eosin Y to act as a direct hydrogen atom transfer catalyst from both synthetic and computational chemistry perspectives.

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Section: Scheme 4 Silane Chlorination Catalyzed By Neutral Eosin Ymentioning

confidence: 99%

Synthetic Applications and Computational Perspectives on Eosin Y Induced Direct HAT Process

Inoa¹,

Dominici²,

Eldabagh³

et al. 2021

Synthesis

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“…Secondary benzylic hydroperoxides are important synthetic precursors for the synthesis of hydroxyl substituted arenes, and act as active oxygen‐atom compounds in oxidation catalysis [4e,f,5d] . Owing to the importance of these precursors, we believed that the desired moiety could be achieved by regioselective ring‐opening reaction of 2‐phenyl aziridine/epoxide 6 with aq.…”

Section: Resultsmentioning

confidence: 99%

Regioselective Hydroperoxylation of Aziridines and Epoxides Only with Aqueous Hydrogen Peroxide

2021

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A catalyst and organic solvent-free regioselective hydroperoxylation of aziridines and epoxides, including spiroaziridine-and spiroepoxy oxindoles have been explored with commercially available 50% aq. H 2 O 2 . This method provides an access to secondary benzylic β-hydroperoxy amines and -alcohols and tertiary 3-hydroperoxy oxindoles. The protocol is also applicable to the less reactive alkyl aziridines. Furthermore, an acid-catalyzed Kornblum-DeLaMare type rearrangement of secondary benzylic hydroperoxide has also been revealed to afford amino-and hydroxyl ketones.

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“…On the other hand, the direct activation and oxidation of the inertness of C(sp 3 )–H bonds, which is the most efficient way to functionalize C–H bonds in the fundamental industry, have been viewed as an appealing sustainable strategy − because it can transform the saturated hydrocarbons into functionalized building blocks to directly obtain various high-added-value fine chemicals . Of the reported light-driven activation and oxidation approaches for the inertness of C(sp 3 )–H bonds, some photocatalysts are able activate substrates without the limitation of redox potentials via a typical hydrogen atom transfer (HAT), which offers enormous opportunities for C–H bond oxidation. , In addition, molecular oxygen, as a cheap and green oxidant, can be activated by photocatalysts to form reactive oxygen species (ROS) for the photo-oxidation of the inert C(sp 3 )–H bond . In terms of the availability, atom economy, and byproduct removal, we envisioned that the integration of the HAT and the ROS generation into one photocatalytic system would prophesy the advent of a novel generation of strategic approaches for direct activation and oxidation of inert C(sp 3 )–H bonds, which is conducive to improving the selectivity and efficiency of photocatalytic systems.…”

Section: Introductionmentioning

confidence: 99%

Anthraquinone-Based Metal–Organic Frameworks as a Bifunctional Photocatalyst for C–H Activation

Zhao

Cai

et al. 2022

Inorg. Chem.

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Metal−organic frameworks (MOFs) have gained attention as multifunctional catalytic platforms, allowing us to gain important insights into synergistically activating both C−H bonds and oxygen for improving oxidation. Herein, by ingenious incorporation of anthraquinone, we report an anthraquinone-based MOF as a bifunctional heterogeneous photocatalytic platform to simultaneously activate inert C(sp 3 )−H bonds and oxygen for C− H bond oxidation. Making use of the rigid framework with the fixation and isolation effect, both a great chemical stability and bifunctional synergistic photocatalytic effects were obtained through the immobilization of anthraquinone into a MOF. Importantly, while decorating two carboxyl groups on anthraquinone, the carbonyl groups of anthraquinone photosensitizers were not involved in coordinating the self-assembly and orderly arranged on the wall of channels that were constructed through a π−π interaction between the anthraquinone moieties in the adjacent layers, which was beneficial to form and stabilize the excited-state radical intermediates in the molecule-fenced channels, and the close proximity between the catalytic sites and the substrates to abstract a hydrogen atom from the substrate through the hydrogen atom transfer process aimed at activating the inertness of C−H bonds. Moreover, highdensity-distributed anthraquinone dyes in the confined channels would activate oxygen to form singlet oxygen ( 1 O 2 ) through an energy transfer pathway, further promoting inert C(sp 3 )−H bond oxidation efficiency. Under visible light irradiation, this anthraquinone-based MOF was successfully applied to explore activation and oxidation of a series of substrates containing benzylic C(sp 3 )−H bonds in the presence of air or oxygen to produce the corresponding carbonyl products. This bifunctional photocatalytic platform based on a heterogeneous MOF provides an available catalytic avenue to develop a scalable and sustainable synthetic strategy using green and sustainable oxygen as the potent oxidant.

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Benzylic Hydroperoxidation via Visible-Light-Induced Csp³–H Activation

Cited by 30 publications

References 42 publications

Synthetic Applications and Computational Perspectives on Eosin Y Induced Direct HAT Process

Synthetic Applications and Computational Perspectives on Eosin Y Induced Direct HAT Process

Regioselective Hydroperoxylation of Aziridines and Epoxides Only with Aqueous Hydrogen Peroxide

Anthraquinone-Based Metal–Organic Frameworks as a Bifunctional Photocatalyst for C–H Activation

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Benzylic Hydroperoxidation via Visible-Light-Induced Csp3–H Activation

Cited by 30 publications

References 42 publications

Synthetic Applications and Computational Perspectives on Eosin Y Induced Direct HAT Process

Synthetic Applications and Computational Perspectives on Eosin Y Induced Direct HAT Process

Regioselective Hydroperoxylation of Aziridines and Epoxides Only with Aqueous Hydrogen Peroxide

Anthraquinone-Based Metal–Organic Frameworks as a Bifunctional Photocatalyst for C–H Activation

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Benzylic Hydroperoxidation via Visible-Light-Induced Csp³–H Activation