Iodosylalkane

Oxidation of alkyl iodides, bearing electron-withdrawing groups such as car-bomethoxy and sulfonyl at the a-carbon, with m-chloroperbenzoic acid results in clean elimination to give olefins [Eq. (27)]. This reaction involves reductive / -elimination of the intermediate iodosylalkanes, as observed in thermal peri-cyclic -elimination of sulfoxides and selenoxides. Exclusive syn stereochemistry in the reductive /1-elimination was established by deuterium labeling... 

The DMDO oxidation of iodocyclohexane affords lran5-2-iodocyclohexanol as the final product via intermediate formation of iodosylcyclohexane followed by elimination of hypoiodous acid, which then adds to the alkene generated in the elimination step [103]. The oxidative deiodination of iodoalkanes via conversion into iodosylalkanes followed by nucleophilic substitution of the iodosyl group has found some synthetic application, particularly in the synthesis of steroidal products (Section 3.1.19) [107]. 

Alkyliodides can be readily oxidized with various oxidizing agents to afford either products of elimination or the products of oxidatively assisted nucleophilic substitution of iodine. Both pathways involve alkyliodine(III) derivatives as reactive intermediates. The elimination pathway generally occurs in reactions of alkyliodides with peracids in a non-nucleophilic solvent, such as dichloromethane [661-663]. Reich and Peake first demonstrated that the elimination proceeds with i yn-stereochemistry and also proposed iodosylalkanes as reactive intermediates in this reaction [661], The Reich iodosyl syn-elimination has been utilized in several syntheses as a very mild and selective elimination method alternative to the standard selenoxide and sulfoxide protocols. 

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