Miscellaneous Carbohydrate Oxidations

For the cw-dihydroxylation of protected lL-l,2 3,4-di-0-isopropylidenecyclohex-5-ene-l,2,3,4-tetrol (22g) to the diol lD-l,2 3,4-di-0-isopropylidene-a/to-inositol by RuClj/aq. Na(IO )/EtOAc-CH3CN/0°C cf. 3.1.2.1 and Fig. 3.3 [347]. Oxygen insertion by stoich. RuO /CCl occurred in addition to the secondary alcohol oxidation of the five-membered ring 5-0-benzoyl-l,2-0-isopropylidene-a-D-xylofnranose, giving the six-membered ring l,2-0-isopropylidene-6-0-benzoyl-3-oxa-a-D-e/7fftro -4-hexulopyranose-a-D-xylofuranose [325]. 

Oxidation of kraft pulp cellulose by aq. RUCI3 or RuO /aq. Na(ClO) or aq. 0.02 M H SOj gave oxycellulose containing carbonyl and carboxylate gronps RuO itself is also effective and is likely to be the principal catalyst [348]. The system RuClj/ Na(Br03)/aq. Na2(C03) pH 9.8 oxidised varions forms of cellnlose [349]. 

For large-scale oxidations of carbohydrates ( Ig) cf. the first column of Table 2.3. For synthesis of carbohydrates by alkene cyclisation cf. 3.1.3.3. 

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Abstract This is one of the most important classes of oxidation effected by Ru complexes, particnlarly by RnO, [RuO ] , [RnO ] and RuCljCPPhj), though in fact most Ru oxidants effect these transformations. The chapter covers oxidation of primary alcohols to aldehydes (section 2.1), and to carboxylic acids (2.2), and of secondary alcohols to ketones (2.3). Oxidation of primary and secondary alcohol functionalities in carbohydrates (sugars) is dealt with in section 2.4, then oxidation of diols and polyols to lactones and acids (2.5). Finally there is a short section on miscellaneous alcohol oxidations in section 2.6. 

Experimental procedures have been described in which the desired reactions have been carried out either by whole microbial cells or by enzymes (1—3). These involve carbohydrates (qv) (4,5) steroids (qv), sterols, and bile acids (6—11) nonsteroid cycHc compounds (12) ahcycHc and alkane hydroxylations (13—16) alkaloids (7,17,18) various pharmaceuticals (qv) (19—21), including antibiotics (19—24) and miscellaneous natural products (25—27). Reviews of the microbial oxidation of aUphatic and aromatic hydrocarbons (qv) (28), monoterpenes (29,30), pesticides (qv) (31,32), lignin (qv) (33,34), flavors and fragrances (35), and other organic molecules (8,12,36,37) have been pubflshed (see Enzyp applications, industrial Enzyt s in organic synthesis Elavors AND spices). 

Most of the compounds that had been reported (before March, 1942) to show cleavage oxidation by periodic acid are recorded in the table the substances are listed alphabetically in the following groups of related compounds (1) carbocyclic compounds (2) carbohydrates (3) a-diketones and a-ketols (4) hydroxyamino compounds (5) polyhydroxy and hydroxyketo acids (6) polyhydroxy alcohols (7) steroids (8) miscellaneous compounds. French journals after May, 1940, and the majority of other foreign publications after June, 1941, were unavailable for the survey. 

Halogen oxidation systems, oxidation potentials of, III, 132 Halogenation, of inositols, III, 57 Halogens, miscellaneous action on carbohydrates, III, 167... 

Miscellaneous Systems Many systems have been mentioned [li,m,2i] acyloxy and acylsilyl phosphine oxides, phosphine sulfides, cyclic compounds, benzoyloxa-ziridine derivatives, dibenzoylmethane derivatives, triazene and pentaazadiene moiety containing compounds. New developments include benzyl benzoin benzyl ethers [112], dithiocarbamates [113], ketoamides [114], phosphonates [115], bromo-acetylpyrene [116], alkylimides [117], aryloxy naphthalene [118], oligosilanes [119], bisphosphine sulfides [120], sulfamic esters of benzoin ethers [121], sulfur [122], or carbohydrate [123] containing compounds. 

Note-. (1-9) Organic acid disorders, (10-14) fatty acid oxidation disorders, (15-20) amino acid disorders, (21-23) hemoglobinopathies, (24 and 25) endocrinopathy, (26) other inborn error of metabolism, (27) carbohydrate disorders, (28) miscellaneous genetic conditions, and (29) infectious diseases. MS/MS tandem mass spectrometry, HPLC high pressure hquid chromatography, lEF isoelectrofocusing, RIA radioimmuno assay, and ELISA enzyme-linked immunosorbent assay. 

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