Selective Oxidation of Organic Compounds—Sustainable Catalytic Reactions with Oxygen and without Transition Metals?

Lenoir, Dieter

doi:10.1002/anie.200502702

Cited by 129 publications

(47 citation statements)

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“…40 Furthermore, oxoammonium oxidations are included in reviews that summarize the following: use of hypervalent iodine reagents for the oxidation of alcohols and their application to complex molecule synthesis, 41 polymersupported organic reagents (including polymer-supported nitroxides), 42 -44 new developments in catalytic oxidations for fine chemicals synthesis, 45,46 polymer reagents in combinatorial chemistry, 47 and catalyzed air oxidations. 48,49 Lastly, a review on the industrial uses of oxidations, including nitroxide-catalyzed reactions, is available. 50 …”

Section: Introductionmentioning

confidence: 99%

Oxoammonium‐ and Nitroxide‐Catalyzed Oxidations of Alcohols

2009

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The discovery in 1959 of stable nitroxide‐based free radicals such as the prototypical 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) led to their use as electron spin resonance (ESR) spin labels in chemistry, biomedicine, and materials science. These nitroxides are prepared by the oxidation of secondary amines that contain no hydrogen atoms on the alpha‐carbons. The unique redox properties of nitroxides enable their use as oxidants in organic synthesis. The varied preparation and uses of oxoammonium salts as stoichiometric oxidants for alcohols are one subject of this review. Oxoammonium ions as oxidants for alcohols have a number of advantages, for example, the method is heavy‐metal free and some of the reactions can be performed in water or aqueous mixtures. A few side reactions are associated with these oxidations. The most serious is the fast reaction of the oxoammonium ion with free amines The several ways these oxidation reactions can be carried out are discussed in detail. They are: Oxidations using stoichimetric quantities of preformed oxoammonium salts carried out in either acidic, neutral, or basic conditions; reactions in which stoichiometric quantities of oxoammonium salts are generated in situ by disproportionation of a nitroxide in the presence of a strong acid; nitroxide‐catalyzed oxidations using a secondary oxidant; efficient nitroxide‐catalyzed oxidations of primary alcohols to carboxylic acids; and oxidations of primary alcohols or hemiacetals that can lead to lactones.

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Section: Introductionmentioning

confidence: 99%

Oxoammonium‐ and Nitroxide‐Catalyzed Oxidations of Alcohols

2009

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“…Since about the mid-1970s, ecological arguments have become more frequent, especially in academic literature, not only to explain the decreasing importance of inorganic oxidizing agents, but also to promote their substitution (or even outright ban) by allegedly "greener" or "more sustainable" oxidants [1]. However, this discussion has often been limited to the nature and cost of the oxidant itself, and very often it has even been misused to simply justify research.…”

Section: Introductionmentioning

confidence: 98%

Oxidation

Teles

Hermans

Franz³

et al. 2015

Ullmann's Encyclopedia of Industrial Chemistry

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The article contains sections titled: 1. Introduction 2. Overview of industrial oxidation processes 2.1. Inorganic chemicals 2.1.1. Sulfur derivatives 2.1.2. Carbon derivatives 2.1.3. Nitrogen derivatives 2.1.4. Chlorine derivatives 2.2. Organic chemicals 2.2.1. Olefins and alkynes 2.2.2. Epoxides 2.2.3. Hydroperoxides 2.2.4. Alcohols 2.2.5. Aldehydes 2.2.6. Ketones 2.2.7. Phenols and derivatives 2.2.8. Carboxylic acids, saturated 2.2.9. Carboxylic acids and anhydrides, unsaturated 2.2.10. Carboxylic acids and anhydrides, aromatic 2.2.11. Esters, lactones and carbonates 2.2.12. Nitriles 2.2.13. Oxidized nitrogen compounds 2.2.14. Chlorinated compounds 2.2.15. Sulfur compounds 3. Thermodynamics; Stability of Hydrocarbons 4. Reaction Types 5. Homolytic Oxidation 5.1. Historical Development; Reaction Mechanism; Radical Reactivity 5.2. Kinetics of Autoxidation 5.3. Differences between Liquid‐ and Gas‐Phase Autoxidations 5.4. Homolytic Oxidation in the Liquid Phase 5.4.1. Secondary Reactions of Radicals, Peroxides, and other Intermediates 5.4.2. Metal Catalysis in Homolytic Liquid‐Phase Oxidation 5.4.3. Inhibitors of Homolytic Liquid‐Phase Oxidation 5.4.4. Special Cases of Homolytic Oxidation 5.4.5. Process Technology of Homolytic Liquid‐Phase Oxidation 5.5. Homolytic Gas‐Phase Oxidation 5.6. Gas Explosions and Safety Data 6. Heterolytic Oxidation 6.1. Heterolytic Oxidation in the Liquid Phase 6.2. Heterogeneously Catalyzed Gas‐Phase Oxidation 6.2.1. Oxidation Catalysts 6.2.2. Process Technology of Heterogeneously Catalyzed Oxidations

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“…The aerobic selective oxidation of alcohols to the corresponding aldehydes and ketones has received great attention, since this important functional group transformations were applied widely both in fundamental synthesis research and industrial manufacturing, and the use of molecular oxygen as terminal oxidant is of economic and environmental benefits [1]. A variety of catalysts and catalytic systems, including homogeneous and heterogeneous type, have been developed for selective aerobic oxidation of alcohols [2,3].…”

Section: Introductionmentioning

confidence: 99%