Trimethylsilyl methanesulfonyl Chloride-Cesium Fluoride

Lac6te, E. Amatore, M. Fensterbank, L. Malacria, M., Synlett lOdl, 116. 

Philippe Dauban Robert H. Dodd Institut de Chimie des Substances Naturelles, Gif-sur-Yvette, France 

InChl = l/C4HllC102SSi/cl-9(2,3)4-8(5,6)7/h4H2,l-3H3 InChIKey = BFUMGFNGDCUBSH-UHFFFAOYAW (CsF) 

Solubility acetonitrile is the preferred solvent due to solubility of CsF and absence of hydrogen bonding Me3SiCH2S02Cl is soluble in most organic solvents. 

Preparative Methods Me3SiCH2S02Cl is (1) formed in 58% isolated yield via reaction of (chloromethyl)trimethylsilane with thiourea in ethanol followed by concentration and chlorination in water, extraction, and distillation . (2) formed in 63% isolated yield by peracetic acid oxidation of (trimethylsi-lyl)methanethiol followed by treatment with phosphorus(V) chloride (3) formed in 84% yield through reaction of Me3-SiCH2Cl with magnesium followed by sequential reaction of the Grignard reagent with sulfur dioxide followed by chlorine and (4) formed in 53% yield through reaction of tetramethylsilane with sulfuryl chloride.  

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One class of reaction evidently missing from this list is the reaction of sulfenes with electrophiles. Sulfene itself is strongly electrophilic and this class may be expected to be small. One class of reaction formally involving a sulfene and an electrophile is the cycloaddition with chloral and related carbonyl compounds. Evidence has been obtained for the importance of tertiary amines in this process and, as is discussed in Section V.B.5, it is unlikely that it is a simple reaction of a sulfene with an electrophile. The reaction of (trimethylsilyl)methanesulfonyl chloride with cesium fluoride in the presence of bromine... 

Sulfenes generated from alkanesulfonyl chlorides and tertiary amines have not been observed to react with simple olefins or dienes1,36, but Block and Aslam98 reported that sulfene from (trimethylsilyl) methanesulfonyl chloride with cesium fluoride reacted with dienes to afford [4 + 2] cycloadducts (equation 110). Slightly greater yields of the... 

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