Secondary alcohols sodium periodate

Phase transfer catalysis can be effective in triphase solid/solid/liquid mixtures. Solid potassium phenoxide and solid sodium iodide react with alkyl halides in the presence of (64). The solid/solid/liquid method also succeeds for hypochlorite oxidation of secondary alcohols and periodate oxidation of glycols catalyzed by commercial AERs (3). 

Two tandem alkene metathesis-oxidation procedures using Grubb s second-generation ruthenium catalyst resulted in unique functional group transformations. Use of sodium periodate and cerium(III) chloride, in acetonitrile-water, furnished cis-diols. Oxidation with Oxone, in the presence of sodium hydrogencarbonate, yielded a-hydroxy ketones.296 Secondary alcohols are oxidized to ketones by a hydrogen... 

A convenient procedure for the reduction of small amounts of ketones involves the periodic addition of small pieces of sodium to a slowly stirred mixture of an ethereal or benzene solution of the ketone and water or a concentrated solution of sodium carbonate. Sodium and alcohol are used for the conversion of methyl n-amyl ketone to 2-heptanol (65%). These reagents are used to prepare secondary alcohols from olefinic ketones obtained by the aldol condensation. Benzophenone and related compounds are reduced by zinc dust and sodium hydroxide, magnesium and methanol, and sodium amalgam. With the last reagent the reaction has been shown to take place through the intermediate sodium ketyl, (C,H,)jCONa. 

The products of the oxidation reactions can be used to distinguish between primary, secondary and tertiary alcohols. A primary alcohol undergoes a two-stage oxidation via an aldehyde to a carboxylic acid, whilst a secondary alcohol gives a ketone. Tertiary alcohols do not react under mild conditions. Potassium permanganate can also be used to oxidize alcohols. 1,2-Diols are oxidized specifically by sodium periodate. 

If a secondary alcohol is not easily oxidized by other methods the ruthenium(Vin) oxide catalyzed procedure is often recommended. As mentioned previously, this is a strong oxidation method which is not compatible with a number of functional groups. Sodium periodate usually serves as the stoichiometric oxidant, but sodium hypochlorite has also been used in the oxidation of secondary alcohols [94]. Because of the cheap oxidants and a straightforward work-up this reaction is well suited for large-scale oxidations [95]. The TEMPO procedure also employs a cheap stoichiometric oxidant and has been applied in the oxidation of 23 on a kilogram scale [87]. The TPAP-catalyzed method is a milder procedure and many functional groups are stable to these conditions. However, secondary alcohols are still oxidized to ketones in high yield with NMO as the co-oxidant [24]. 

Osmium tetroxide [1, 759-764, before references]. On oxidation of gibberellin A14 dimethyl ester (1) with osmium tetroxide in pyridine, followed by sodium periodate, Cross13 obtained the expected norketone (2) as the major product but also isolated a small quantity of (3), a product of further oxidation of the secondary hydroxyl group present. A footnote states that several similar examples of the oxidation of secondary alcohols by osmium tetroxide have been encountered. ... 

To construct tricycHc compound 275, they first employed sodium boro-hydride to reduce the keto group to furnish alcohol 273. The terminal olefin was then converted to an alcohol via a two-step protocol employing oxidation with osmium tetroxide and sodium periodate followed by reduction with sodium borohydride to furnish diol 274, which underwent acid mediated lactonization. Dess—Martin oxidation of the remaining secondary alcohol then led to the desired tricyclic lactone 275. 

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