Chloromethyl Trimethylsilylmethyl Sulfide


[105850-89-3]  · C5H13ClSSi  · Chloromethyl Trimethylsilylmethyl Sulfide  · (MW 168.76)

(thiocarbonyl ylide synthon1)

Physical Data: bp 75 °C/20 mmHg.

Solubility: sol acetonitrile, THF.

Preparative Method: prepared in 69% yield by introducing dry Hydrogen Chloride into a mixture of trimethylsilylmethanethiol2 and 1,3,5-trioxane (see Formaldehyde) at temperature below 0 °C.3

Purification: by distillation.

Handling, Storage, and Precautions: potent alkylating agent; moisture sensitive; stench; use in a fume hood.

Stereospecific [3 + 2] annulation of chloromethyl trimethylsilylmethyl sulfide (1) with electron-deficient alkenes in the presence of Cesium Fluoride in acetonitrile at room temperature gives tetrahydrothiophenes in good yields (eq 1).3 This reaction presumably goes through thiocarbonyl ylide intermediate (2).

Sulfide (1) also reacts with acetylenedicarboxylate to give the corresponding dihydrothiophenes.3 However, (1) is not reactive towards cyclic alkenes such as maleic anhydride.

The title reagent also reacts with aromatic aldehydes to yield the corresponding [3 + 2] cycloadduct 1,3-oxathiolanes (eq 2).4 Simple ketones and oxoesters do not undergo this reaction.

When sulfide (1) is heated with nitrogen-containing aromatic heterocycles followed by treatment with cesium fluoride in acetonitrile, various 1,3-thiazolidines are obtained (eq 3).1 This is formally a [3 + 2] cycloaddition between the thiocarbonyl ylide (2) and the carbon-nitrogen double bond.

1. Hosomi, A.; Hayashi, S.; Hoashi, K.; Kohra, S.; Tominaga, Y. JOC 1987, 52, 4423.
2. Noller, D. C.; Post, H. W. JOC 1952, 17, 1393.
3. Hosomi, A.; Matsuyama, Y.; Sakurai, H. CC 1986, 1073.
4. Hosomi, A.; Hayashi, S.; Hoashi, K.; Kohra, S.; Tominaga, Y. CC 1987, 1442.

Yeun-Min Tsai

National Taiwan University, Taipei, Republic of China

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