Oxidation-reduction reactions overview

In order to place later chapters in proper context, the first chapter offers a comprehensive overview of industrially important catalysts for oxidation and reduction reactions. Chapters 2 and 3 describe the preparation of chiral materials by way of the asymmetric reduction of alkenes and ketones respectively. These two areas have enjoyed a significant amount of attention in recent years. Optically active amines can be prepared by imine reduction using chiral catalysts, as featured in Chapter 4, which also discloses a novel reductive amination protocol. 

Inter-conversions between the compounds listed in Table 1-1 are possible and often occur readily. The oxide hydroxides dehydrate to their anhydrous structural counterparts and ultimately to hematite on heating. At lower temperatures and in solution, inter-conversions usually require dissolution followed by reprecipitation of the new phase. Oxidation or reduction reactions are also possible. An overview of the more frequent inter-conversions is presented in Fig. 1-2. 

Oxidation and reduction are fundamental processes in the synthesis of organic and inorganic compounds. Some oxidation and reduction reactions are difficult to control in macro-scale batch reactors and in such cases microflow reactors serve as powerful tools for accomplishing the reactions in a highly controlled manner. This is especially true for many oxidation reactions because of their exothermic nature. It should also be noted that the danger of unexpected explosions can be avoided by the use of microflow reactors because of the small volume and highly efficient heat transfer ability of microflow systems. This chapter provides an overview of oxidation and reduction reactions using chemical, electrochemical and biochemical methods in microflow reactors. 

Abstract A review is provided on the contribution of modern surface-science studies to the understanding of the kinetics of DeNOx catalytic processes. A brief overview of the knowledge available on the adsorption of the nitrogen oxide reactants, with specific emphasis on NO, is provided first. A presentation of the measurements of NO, reduction kinetics carried out on well-characterized model system and on their implications on practical catalytic processes follows. Focus is placed on isothermal measurements using either molecular beams or atmospheric pressure environments. That discussion is then complemented with a review of the published research on the identification of the key reaction intermediates and on the determination of the nature of the active sites under realistic conditions. The link between surface-science studies and molecular computational modeling such as DFT calculations, and, more generally, the relevance of the studies performed under ultra-high vacuum to more realistic conditions, is also discussed. 

Despite the diverse range of documented enzyme-catalyzed reactions, there are only certain types of transformations that have thus far emerged as synthetically useful. These reactions are the hydrolysis of esters, reduction/oxidation reactions, and the formation of carbon-carbon bonds. The first part of this chapter gives a brief overview by describing some examples of various biotransformations that can easily be handled and accessed by synthetic organic chemists. These processes are now attracting more and more attention from nonspecialists of enzymes. 

See also Biotransformations Microbial oxidations Microbial reductions applications of, 76 396-399 biocatalyst selection in, 76 404-409 biocatalysts in, 76 409-414 for drug metabolite production, 76 398-399 further advances in, 76 414 in hydrolysis, 76 400-401 multiphase reactions in, 777 412-414 scale-up of, 76 414 systematic studies of, 76 398 technique overview for, 76 403-414 timing of substrate additions in, 76 411-412 uses for, 777 400-403 Microbial waxes, 26 203 Microbiocides, triorganotins as, 24 817 Microbiological culture media, agar in, 73 68... 

A broad spectrum of chemical reactions can be catalyzed by enzymes Hydrolysis, esterification, isomerization, addition and elimination, alkylation and dealkylation, halogenation and dehalogenation, and oxidation and reduction. The last reactions are catalyzed by redox enzymes, which are classified as oxidoreductases and divided into four categories according to the oxidant they utilize and the reactions they catalyze 1) dehydrogenases (reductases), 2) oxidases, 3) oxygenases (mono- and dioxygenases), and 4) peroxidases. The latter enzymes have received extensive attention in the last years as bio catalysts for synthetic applications. Peroxidases catalyze the oxidation of aromatic compounds, oxidation of heteroatom compounds, epoxidation, and the enantio-selective reduction of racemic hydroperoxides. In this article, a short overview... 

Aliphatic nitro compounds are versatile building blocks and intermediates in organic synthesis,14 15 cf. the overview given in the Organic Syntheses preparation of nitroacetaldehyde diethyl acetal.16 For example, Henry and Michael additions, respectively, lead to 1,2- and 1,4-difunctionalized derivatives.14 18 1,3-Difunctional compounds, such as amino alcohols or aldols are accessible from primary nitroalkanes by dehydration/1,3-dipolar nitrile oxide cycloaddition with olefins (Mukaiyama reaction),19 followed by ring cleavage of intermediate isoxazolines by reduction or reduction/hydrolysis.20 21... 

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