Inside Cover: Radical Acylfluoroalkylation of Olefins through N‐Heterocyclic Carbene Organocatalysis (Angew. Chem. Int. Ed. 5/2020)

Li, Jun‐Long; Liu, Yanqing; Zou, Wen‐Lin; Zeng, Rong; Zhang, Xiang; Liu, Yue; Han, Bo; He, Yanfang; Leng, Hai‐Jun; Li, Qing‐Zhu

doi:10.1002/anie.201915594

Cited by 7 publications

(12 citation statements)

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“…As an important reaction intermediate, the adsorption strength of *CH 3 OCOO on the catalyst surface significantly affects its subsequent dissociation and conversion. Based on the recent reports, the stronger adsorbed *CH 3 OCOO on oxygen vacancy enriched CeO 2 is more easily dissociated, but the*CH 3 OCOO formation is the rate determining‐step (RDS) [7,11] . Therefore, the weak *CH 3 OCOO adsorption and high catalytic performance of CeO 2 ‐600 suggested the different reaction routes compared to oxygen vacancy enriched CeO 2 .…”

Section: Resultsmentioning

confidence: 99%

“…Based on the recent reports, the stronger adsorbed *CH 3 OCOO on oxygen vacancy enriched CeO 2 is more easily dissociated, but the*CH 3 OCOO formation is the rate determining-step (RDS). [7,11] Therefore, the weak *CH 3 OCOO adsorption and high catalytic performance of CeO 2 -600 suggested the different reaction routes compared to oxygen vacancy enriched CeO 2 . Therefore, we speculate that the RDS has been changed on CeO 2 -600.…”

Section: Methodsmentioning

confidence: 99%

“…[6] The introduction of surface oxygen vacancies on CeO 2 was taken as an effective strategy to activate CO 2 molecules and enhance the DMC yield. [7] For example, Liu et al attributed a 12 mmol g À 1 increase in DMC yield on Zr 0.1 Ce nanorod with higher concentration of oxygen vacancy. [4a] Kuan et al applied a reflux approach to enrich the oxygen vacancy on defective mesoporous CeO 2 nanorod catalysts.…”

Section: Introductionmentioning

confidence: 99%

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Dimethyl Carbonate Synthesis from CO₂ over CeO₂ with Electron‐Enriched Lattice Oxygen Species

Hou,

Wang,

et al. 2024

Angewandte Chemie

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The direct synthesis of dimethyl carbonate (DMC) from CO2 has both theoretical and practical value in carbon neutrality, but its efficiency is far from the application requirements due to the lacks of understanding of reaction mechanism and rational design of catalyst. Herein, abundant electron‐enriched lattice oxygen species were introduced into CeO2 catalyst by constructing a large number of point defects and crystal‐terminated phases in the crystal reconstruction process. Benefitting from the modulation of acid‐base properties by electron‐enriched lattice oxygen, a much higher DMC yield of 22.2 mmol g‐1 was achieved on optimized CeO2 catalyst than other reported metal‐oxide‐based catalysts at similar conditions. Mechanistic investigations illustrated that the electron‐enriched lattice oxygen, instead of the oxygen vacancy, not only provided abundant sites for CO2 adsorption and activation, but also significantly induced the weakly absorbed methoxy species formation. Both of which facilitated the coupling of methoxy and CO2 to *CH3OCOO intermediate. In addition, the *CH3OCOO adsorption was obviously weakened on electron‐enriched lattice oxygen, thus shifting the rate‐determining‐step (RDS) from *CH3OCOO formation to *CH3OCOO dissociation and lowing the reaction energy barrier. This work provides insight into the underlying reaction mechanism for DMC synthesis from CO2 and methanol and the design of highly active catalysts.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Dimethyl Carbonate Synthesis from CO₂ over CeO₂ with Electron‐Enriched Lattice Oxygen Species

Hou,

Wang,

et al. 2024

Angewandte Chemie

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“…Using the same strategy of SET reduction between deprotonated Breslow intermediates and alkyl halides, multitudinous methodologies involving radical-relay have been developed by Li, [21] Wu, [22] Ohmiya, [23] Ye, [24] and Du, [25] achieving the threecomponent radical coupling reaction of aldehydes, alkenes and activated alkyl halides (Scheme 5a-5e). All those protocols feature mild reaction conditions and broad substrates, especially for some bioactive fragments, such as fenofibrate derivative 20 a, menthol derivative 30 b, and cholesterol derivative 30 c in moderate to excellent yields.…”

Section: Coupling Reactions Of Aldehydes Organic Halides and Alkenes ...mentioning

confidence: 99%

N‐Heterocyclic Carbenes (NHCs)‐Catalyzed Coupling Reactions of Aldehydes and Organic Halides

Gao,

Zhang,

Yan

2024

ChemCatChem

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This concept aims to summarize the direct coupling of aldehydes and organic halides (including activated and unactivated organic halides) catalyzed by N‐heterocyclic carbenes (NHCs). The key factor of this transformation is the formation of Breslow intermediates, which are either nucleophilic or reductive. Additionally, the activation of inert C‐H bond also was reviewed in this performance via the processes of single electron transfer (SET) and subsequent intramolecular 1,n‐ hydrogen atom transfer (HAT) or intermolecular HAT. Finally, the key differences and reactivity of various Breslow intermediates, generated from different NHCs, have been discussed to give a deeper understanding of the ongoing popularity of the NHC‐organocatalysis.

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“…Moreover, it facilitated the removal of CO, thus inhibiting the reaction of CH 4 . Gersappe et al [26] . constructed dual‐active sites comprised of Pt clusters and FLPs on the surface of porous CeO 2 nanorods (Pt cluster /PN−CeO 2 ) to enable interface‐independent RWGS with high activity and selectivity as well as remarkable stability at low temperatures (<350 °C).…”

Section: Noble Metal Catalysts For Rwgs Reactionsmentioning

confidence: 99%

Recent Advances in Hydrogenation of CO₂ to CO with Heterogeneous Catalysts Through the RWGS Reaction

Zhang,

Sun,

Wang

et al. 2024

Chemistry An Asian Journal

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With the continuous increase in CO2 emissions, primarily from the combustion of coal and oil, the ecosystem faces a significant threat. Therefore, as an effective method to minimize the issue, Reverse Water Gas Shift (RWGS) reaction which converts CO2 towards CO attracts much attention, is an environmentally‐friendly method to mitigate climate change and lessen dependence on fossil fuels. Nevertheless, the inherent thermodynamic stability and kinetic inertness of CO2 is a big challenge under mild conditions. In addition, it remains another fundamental challenge in RWGS reaction owing to CO selectivity issue caused by CO2 further hydrogenation towards CH4. Up till now, a series of catalysis systems have been developed for CO2 and H2 reduction reaction to produce CO. Herein, the research progress of the well‐performed heterogeneous catalysts for the RWGS reaction were summarized, including the catalyst design, catalytic performance and reaction mechanism. This review will provide insight into efficient utilization of CO2 and will promote the development of RWGS reaction.

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Inside Cover: Radical Acylfluoroalkylation of Olefins through N‐Heterocyclic Carbene Organocatalysis (Angew. Chem. Int. Ed. 5/2020)

Cited by 7 publications

References 0 publications

Dimethyl Carbonate Synthesis from CO₂ over CeO₂ with Electron‐Enriched Lattice Oxygen Species

Dimethyl Carbonate Synthesis from CO₂ over CeO₂ with Electron‐Enriched Lattice Oxygen Species

N‐Heterocyclic Carbenes (NHCs)‐Catalyzed Coupling Reactions of Aldehydes and Organic Halides

Recent Advances in Hydrogenation of CO₂ to CO with Heterogeneous Catalysts Through the RWGS Reaction

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Inside Cover: Radical Acylfluoroalkylation of Olefins through N‐Heterocyclic Carbene Organocatalysis (Angew. Chem. Int. Ed. 5/2020)

Cited by 7 publications

References 0 publications

Dimethyl Carbonate Synthesis from CO2 over CeO2 with Electron‐Enriched Lattice Oxygen Species

Dimethyl Carbonate Synthesis from CO2 over CeO2 with Electron‐Enriched Lattice Oxygen Species

N‐Heterocyclic Carbenes (NHCs)‐Catalyzed Coupling Reactions of Aldehydes and Organic Halides

Recent Advances in Hydrogenation of CO2 to CO with Heterogeneous Catalysts Through the RWGS Reaction

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Product

Resources

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Dimethyl Carbonate Synthesis from CO₂ over CeO₂ with Electron‐Enriched Lattice Oxygen Species

Dimethyl Carbonate Synthesis from CO₂ over CeO₂ with Electron‐Enriched Lattice Oxygen Species

Recent Advances in Hydrogenation of CO₂ to CO with Heterogeneous Catalysts Through the RWGS Reaction