Chlorotrimethylsilane, reaction with sodium iodide

The structurally simplest silicon reagent that has been used to reduce sulphoxides is the carbene analog, dimethylsilylene (Me2Si )29. This molecule was used as a mechanistic probe and did not appear to be useful synthetically. Other silanes that have been used to reduce sulphoxides include iodotrimethylsilane, which is selective but unstable, and chlorotrimethylsilane in the presence of sodium iodide, which is easy to use, but is unselective since it cleaves esters, lactones and ethers it also converts alcohols into iodides. To circumvent these complications, Olah30 has developed the use of methyltrichlorosilane, again in the presence of sodium iodide, in dry acetonitrile (equation 8). A standard range of sulphoxides was reduced under mild conditions, with yields between 80 and 95% and with a simple workup process. The mechanism for the reaction is probably very similar to that given in equation (6), if the tricoordinate boron atoms in this reaction scheme are replaced... 

Iodotrimethylsilane formed in situ from the reaction of chlorotrimethylsilane and sodium iodide, also effects the conversion of 2-ene-l,4-diols to 1,3-dienes (equation 16)46. Allylic thionocarbonates on heating with triphenylphosphite undergo deoxygenation (Corey-Winter reaction) to generate olefins47. This procedure has been used for making hexatrienes (equation 17)47b. 

Two new modifications of the synthesis of olefins from vicinal diols have appeared in the literature. Barua and Sharma have demonstrated that both cis and fra/M-secondary-tertiary 1,2-diols are readily converted (in a mild manner, and in excellent yields) into olefins by using chlorotrimethylsilane and sodium iodide in acetonitrile at room temperature, Corey and Hopkins have improved the thionocarbonate olefin s mthesis by modification of the reaction conditions to allow sensitive and complex diols to be converted into olefins. Thus, the reaction of 1,2-diols with thiophosgene affords the thionocarbonates (39) in... 

Olah GA, Narang SC, GuptaBGB et al (1979) Synthetic methods and reactions. 62. Transformations with chlorotrimethylsilane/sodium iodide, a convenient in situ iodotrimethylsilane reagent J Oig Chem 44 1247-1251... 

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