Transition metal ion catalysed autoxidation of dimethylformamide

Dhar, S.K.; Abdelaziz, Jamal; Cožži, Phillip J.; Jasien, Paul G.; Mason, Carol A.; Zalenas, Robert

doi:10.1039/c3984000008b

Cited by 6 publications

(5 citation statements)

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“…Moreover, CuOAc and Cu(OAc) 2 gave very similar results in terms of product yield and distribution (Table , entry 27; Table , entry 8). These seem to be pointing out the necessity of the formation of corresponding Cu(I) salts that are either chiefly active species or act together with Cu(II) salts . This could be understandable if one considers that highly electronegative ligands (triflate and trifluoroacetate) may retard the reduction of the presumably inactive Cu(II) salts to the corresponding Cu(I) salts (which were shown to be active), even though chloride does not perfectly fit into this picture.…”

Section: Resultsmentioning

confidence: 99%

Role of Copper Species in the Oxidative Dimerization of Arylboronic Acids: Synthesis of Symmetrical Biaryls

2003

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Section: Resultsmentioning

confidence: 99%

Role of Copper Species in the Oxidative Dimerization of Arylboronic Acids: Synthesis of Symmetrical Biaryls

2003

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“…The possible role of DMF to reduce the catalyst and restart the catalytic cycle has also been postulated [109] . Furthermore, the formation of hydroperoxides from dialkyl amides upon exposure to O 2 , their decomposition and activity as oxidants have been studied in detail and are known to be catalyzed by transition metal cations [102–103,110] . The C−H bonds in N,N‐dialkyl amides are labile and easily broken by oxygen‐centered radicals, [111] making the H abstraction by radical intermediates possible.…”

Section: Thermal Catalysismentioning

confidence: 99%

“…In addition, the stability and reactivity of the solvent under reaction conditions are also rather important. Solvents in liquid‐phase oxidations are often non‐innocent, being oxidized or reduced during the reaction, and may even serve as the actual oxidants [102–103] . Mallat and Baiker [102] identified an unusual high solvent specificity and unexpected byproducts as warning signs for non‐inert solvents.…”

Section: Thermal Catalysismentioning

confidence: 99%

“…Solvents in liquid‐phase oxidations are often non‐innocent, being oxidized or reduced during the reaction, and may even serve as the actual oxidants. [ 102 , 103 ] Mallat and Baiker [102] identified an unusual high solvent specificity and unexpected byproducts as warning signs for non‐inert solvents. If the solvent is not considered in these cases, erroneous mechanistic conclusions are inevitable.…”

Section: Thermal Catalysismentioning

confidence: 99%

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A Perspective on Heterogeneous Catalysts for the Selective Oxidation of Alcohols

Najafishirtari

Ortega

Douthwaite

et al. 2021

Chemistry A European J

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Selective oxidation of higher alcohols using heterogeneous catalysts is an important reaction in the synthesis of fine chemicals with added value. Though the process for primary alcohol oxidation is industrially established, there is still a lack of fundamental understanding considering the complexity of the catalysts and their dynamics under reaction conditions, especially when higher alcohols and liquid-phase reaction media are involved. Additionally, new materials should be developed offering higher activity, selectivity, and stability. This can be achieved by unraveling the structure-performance correlations of these catalysts under reaction conditions. In this regard, researchers are encouraged to develop more advanced characterization techniques to address the complex interplay between the solid surface, the dissolved reactants, and the solvent. In this mini-review, we report some of the most important approaches taken in the field and give a perspective on how to tackle the complex challenges for different approaches in alcohol oxidation while providing insight into the remaining challenges.

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“…The autoxidation of amides is accelerated by transition metal ions. [136][137][138] Decomposition of the 1-amidoalkyl hydroperoxide gives various products, depending on the conditions and the catalyst. In the epoxidation of styrene with oxygen and CoHAp catalyst, N-formyl-N-methylformamide (FMF, Scheme 9) was produced in a considerable amount.…”

Section: Dimethyl Sulfoxide the ''Sacrificial'' Solventmentioning

confidence: 99%

Reactions in “sacrificial” solvents

Mallát

Baiker

2011

Catal. Sci. Technol.

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The involvement of organic solvents in redox reactions and their influence on the efficiency and ''greenness'' of the desired chemical transformation are critically reviewed. Some representative examples are presented on the co-oxidation and co-reduction of widely used solvents (alcohols, ethers, nitriles, amides, sulfoxides, hydrocarbons, dense CO 2 ), and on the impact of these frequently hidden reactions. The transformation of the solvent may be limited to its unintended consumption leading to an increase in the E-factor, but it may also play a critical role in the reaction investigated and lead to false interpretation of reaction mechanisms. In fact, the approach of using a ''sacrificial'' solvent as a part of the oxidizing system may be an attractive-but surely not a green-alternative in synthetic chemistry. Finally, the crucial but often unrecognized role of the solvent in stabilizing or destabilizing catalytic metal nanoparticles is discussed. Surface redox reactions involving the solvent can be decisive for switching between heterogeneous and homogeneous catalytic pathways.

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Transition metal ion catalysed autoxidation of dimethylformamide

Cited by 6 publications

References 0 publications

Role of Copper Species in the Oxidative Dimerization of Arylboronic Acids: Synthesis of Symmetrical Biaryls

Role of Copper Species in the Oxidative Dimerization of Arylboronic Acids: Synthesis of Symmetrical Biaryls

A Perspective on Heterogeneous Catalysts for the Selective Oxidation of Alcohols

Reactions in “sacrificial” solvents

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