Alcohols, secondary, oxidation with Raney nickel

Catalytic Oxidation of Secondary Alcohols with Raney Nickel in Presence of Cyclohexanone... 

The chemistry of rran5-4-r-butyl(diphenyl)silyloxythiane oxide has been investigated by Simpkins in the synthesis of protected, substituted secondary alcohols. Simpkins has found that the anion of fra s-4-r-butyl(diphenyl) silyloxythiane oxide, when treated with trimethylsilyl chloride, can form a 2,4-disubstituted thiane in turn, this product may be easily desulfurized with Raney nickel to liberate (S)-3-r-butyl(diphenyl)silyloxy-l-trimethylsilylpentane in good yield (Scheme 4.49) [101]. 

Reaction of the bicyclic 1,3,4-oxadithiolane (113) with triphenylphosphine in refluxing toluene led to an equilibrium mixture of the 1,3-oxathietane (114) and the thiocarbonyl derivative (115) (Scheme 29) <93BCJ1714>. Raney nickel can be used to desulfurize both 1,2,4-trithiolanes (to methylene compounds) and 5,5-disubstituted 1,2,4-oxadithiolane 2-oxides (116) which give rise to secondary alcohols (Equation (20)) <90BSB265>. 

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