Selective C(sp3)−H Functionalization of Alkyl Esters with N‐/S‐/O‐Nucleophiles Using Perfluoroalkyl Iodide as Oxidant

Zhao, Shi-Wen; Cai, Song-Zhou; Wang, Mao‐Lin; Rao, Weidong; Xu, Haiyan; Zhang, Lei; Chu, Xue‐Qiang; Shen, Zhi‐Liang

doi:10.1002/adsc.202000199

Cited by 9 publications

(1 citation statement)

References 52 publications

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“…Additionally, Zhao et al. observed that, for the liquid phase hydrogenation of toluene over Pd/SiO 2 , a hydrophylic solvent adsorbed strongly on the support strongly limiting the hydrocarbon conversion [55] . Another study by Bertero et al.…”

Section: Resultsmentioning

confidence: 99%

Role of Catalyst Support's Physicochemical Properties on Catalytic Transfer Hydrogenation over Palladium Catalysts

et al. 2021

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Catalytic transfer hydrogenation (CTH) is a promising reaction for valorisation of bio‐based feedstocks via hydrogenation without needing to use H2. Unlike standard hydrogenation, CTH occurs via dehydrogenation (DHD) of a hydrogen donor (H‐donor) and hydrogenation (HYD) of a substrate. Therefore, the “ideal” CTH catalyst must balance the catalysis of both reactions to maximize the hydrogen transfer between H‐donor and substrate with minimal H2 loss to gas (high atom efficiency). Additionally, the H‐donor must be highly stable to prevent secondary reactions with the substrate. Herein we study the impact of the catalyst's properties on CTH of guaiacol using bicyclohexyl, a liquid organic hydrogen carrier, as a H‐donor. The reaction was promoted by palladium dispersed on three typical support materials (γ‐Al2O3, MgO, and SiO2). The performance of these catalysts in the conversion of bicyclohexyl and guaiacol was evaluated, allowing to estimate the H‐transfer efficiency, as well as the potential for recycling the spent H‐donor (bicyclohexyl). The apparent activation energies for DHD of bicyclohexyl and HYD of guaiacol revealed that slow DHD combined with fast HYD, as is the case with Pd/MgO, favours hydrogen transfer efficiency and selectivity towards hydrogenated products. In addition, an investigation of the DHD of bicyclohexyl and HYD of guaiacol independently showed that the affinity between the organic molecules and the support significantly impacts CTH. Indeed, Pd/SiO2 was highly active for both reactions individually and almost inactive for CTH. Consequently, these findings highlight the importance of the interaction between solvent‐substrate‐support in designing catalysts for transfer hydrogenation.

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Section: Resultsmentioning

confidence: 99%

Role of Catalyst Support's Physicochemical Properties on Catalytic Transfer Hydrogenation over Palladium Catalysts

et al. 2021

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Metal‐Free Oxidative Double C(sp³)−C(sp³) Coupling of 1,3‐Dicarbonyl Compounds and N,N‐Dimethylanilines

et al. 2020

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N‐Oxyl Radicals in Oxidative C−O Coupling: Free‐Radical Hydrogen Substitution and Addition to C=C Bonds

Lopat'eva,

Krylov,

et al. 2024

Asian J Org Chem

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N‐oxyl radicals occupy an important place in free‐radical oxidative CH‐functionalization being one of the most efficient redox‐organocatalysts for hydrogen atom abstraction (HAT). Their applications include aerobic radical chain autoxidation, CH‐functionalization with the formation of carbon‐carbon and carbon‐heteroatom bonds. The persistent nature of N‐oxyl radicals combined with their high reactivity in HAT results in their unique dual chemistry: the same radical can both propagate radical chain reaction (at low N‐oxyl concentrations) and effectively “terminate” carbon‐centered radicals (at higher N‐oxyl concentrations). The latter case opens a new synthetic application area of N‐oxyl radicals, in which they act as both hydrogen abstracting species and O‐reagents for cross‐coupling with carbon‐centered radicals thus produced. Apart from the C–H bond cleavage, reactive N‐oxyl radicals have been extensively used recently in C=C double bond functionalization via radical addition reactions. In this review, both free‐radical CH‐functionalization reactions with the introduction of N‐oxyl fragments and alkene difunctionalizations by N‐oxyls are covered with emphasis on the relationship between reaction conditions and selectivity.

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Selective C(sp³)−H Functionalization of Alkyl Esters with N‐/S‐/O‐Nucleophiles Using Perfluoroalkyl Iodide as Oxidant

Cited by 9 publications

References 52 publications

Role of Catalyst Support's Physicochemical Properties on Catalytic Transfer Hydrogenation over Palladium Catalysts

Role of Catalyst Support's Physicochemical Properties on Catalytic Transfer Hydrogenation over Palladium Catalysts

Metal‐Free Oxidative Double C(sp³)−C(sp³) Coupling of 1,3‐Dicarbonyl Compounds and N,N‐Dimethylanilines

N‐Oxyl Radicals in Oxidative C−O Coupling: Free‐Radical Hydrogen Substitution and Addition to C=C Bonds

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Selective C(sp3)−H Functionalization of Alkyl Esters with N‐/S‐/O‐Nucleophiles Using Perfluoroalkyl Iodide as Oxidant

Cited by 9 publications

References 52 publications

Role of Catalyst Support's Physicochemical Properties on Catalytic Transfer Hydrogenation over Palladium Catalysts

Role of Catalyst Support's Physicochemical Properties on Catalytic Transfer Hydrogenation over Palladium Catalysts

Metal‐Free Oxidative Double C(sp3)−C(sp3) Coupling of 1,3‐Dicarbonyl Compounds and N,N‐Dimethylanilines

N‐Oxyl Radicals in Oxidative C−O Coupling: Free‐Radical Hydrogen Substitution and Addition to C=C Bonds

Contact Info

Product

Resources

About

Selective C(sp³)−H Functionalization of Alkyl Esters with N‐/S‐/O‐Nucleophiles Using Perfluoroalkyl Iodide as Oxidant

Metal‐Free Oxidative Double C(sp³)−C(sp³) Coupling of 1,3‐Dicarbonyl Compounds and N,N‐Dimethylanilines