Carbonyl compounds dimethyl sulfoxide-iodide

Trichloro(methyl)silane-Sodium iodide, 11, 553-554. This in situ equivalent of io-dotrimethylsilane is also effective for cleavage of esters and lactones, selective conversion of tertiary and benzylic aleohols into iodides, dehalogenation of a-halo ketones, deoxygenation of sulfoxides, and conversion of dimethyl acetals to carbonyl compounds. ... 

Dimethyl sulfoxide-derived reagent (c). Dimethyloxosulfonium methylide, (C H. i)2S=C H 2. This more stable reagent introduced by Corey reacts with monofunctional carbonyl compounds to give epoxides (oxiranes), but with a,/3-unsaturated ketones it gives cyclopropyl ketones. In one procedure a mixture of 0.1 mole each of powdered sodium hydride and trimethyloxosulfonium iodide (I) - is placed in a three-... 

Related to these reactions is the oxidation of alkyl halides or tosylates to carbonyl compounds with dimethyl sulfoxide (or trimethylammonium A/-oxide). The reaction is effected simply by warming the halide (normally the iodide) or sulfonate in DMSO (or MeaNO), generally in the presence of a proton acceptor such as sodium hydrogen carbonate or a tertiary amine. Oxidation never proceeds beyond the carbonyl stage and other functional groups are unaffected. The reaction has been applied to benzyl halides, phenacyl halides, primary sulfonates and iodides and a limited number of secondary sulfonates. With substrates containing a secondary rather than primary halide or sulfonate elimination becomes an important side reaction and the oxidation is less useful with such compounds. 

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