Manganese organisms transforming

Transition metal ions such as iron, copper, manganese, and zinc are found in much lower concentrations, at most a few ppm, in drinking water. However, they can be found at much higher levels in untreated water. Although found at much lower levels than hardness ions, transition metals can be chemically active and catalyze a host of organic transformations. The poweroftransitionmetal catalysis isharnessed by Nature, inmany enzymes, and in the chemical industry, to facilitate various chemical reactions. 

The following segment on the reactivity of manganese complexes will be broken into two sections. The first will cover some of the areas that compose research into the reactivity of manganese-based systems as applied to a specific synthetic organic transformation. The second segment will concentrate on systems designed specifically to model the reactivity of particular enzyme systems. 

Previous reviews have dealt with metal-catalyzed [93] and stoichiometric [94] oxidation of amines in a broad sense. This section will be limited to the selective oxidation of tertiary amines to N-oxides. Amine N-oxides are synthetically useful compounds [95, 96] and are frequently used as stoichiometric oxidants in osmium-[97-99] manganese- [100] and ruthenium-catalyzed [101,102] oxidations, as well as in other organic transformations [103-105]. Aliphatic tert-amine N-oxides are usefid surfactants [96] and are essential components in hair conditioners, shampoos, toothpaste, cosmetics, and so on [106]. Chiral N-oxides have been used in asymmetric catalysis involving metal-free catalytic transformations [107] as well as metal-catalyzed reactions where the N-oxide serves as a ligand [107, 108]. Chiral tertiary amine N-oxides were recently used as reagents in asymmetric epoxidation of a,(3-unsaturated ketones [109]. 

The oxidation of organic compounds by manganese dioxide has recently been reviewed. It is of limited application for the introduction of double bonds, but the advantages of mildness and simple workup make it attractive for some laboratory-scale transformations. Manganese dioxide is similar to chloranil in that it will oxidize A -3-ketones to A -dienones in refluxing benzene. Unfortunately, this reaction does not normally go to completion, and the separation of product from starting material is difficult. However, Sondheimer found that A -3-alcohols are converted into A -3-ketones, and in this instance separation is easier, but conversions are only 30%. (cf. Harrison s report that manganese dioxide in DMF or pyridine at room temperature very slowly converts A -3-alcohols to A -3-ketones.)... 

Soil pH affects the transformation of Cr between Cr(III) and Cr(VI) in soils. Since Cr(VI) has greater bioavailability and mobility in soils than Cr(III), which is strongly bound by soil solid matrix (Han and Banin, 1997). Cr(III) can be oxidized by soil manganese oxides into Cr(VI), while Cr(VI) can be reduced by organic matter, Fe(II) and microorganisms in soils. Reduction of Cr(VI) has been found to occur much slower in alkaline soils compared to acid soils (Cary et al., 1997). 

Mandal L.N., Mitra R.R. Transformation of iron and manganese in rice soils under different moisture regimes and organic matter applications. Pland Soil 1982 69 45-56. 

The oxidation of alcohols to the corresponding aldehydes, ketones or acids certainly represents one of the more important functional group transformations in organic synthesis and there are numerous methods reported in the literature (1-3). However, relatively few methods describe the selective oxidation of primary or secondary alcohols to the corresponding aldehydes and ketones and most of them traditionally use a stoichiometric terminal oxidant such as chromium oxide (4), dichromate (5), manganese oxide (6), and osmium or ruthenium oxides as primary oxidants (7). 

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