Markovic, DeanTchawou, Wandji AugustinNovosjolova, IrinaLaclef, SylvainStepanovs, DmitrijsTurks, MarisVogel, Pierre2016-07-192016-07-192016-07-19201610.1002/chem.201504380https://infoscience.epfl.ch/handle/20.500.14299/127419WOS:000372526500037Trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, and triisopropylsilyl 2-methylprop-2-ene-1-sulfinates were prepared through (CuOTf)(2)C6H6-catalyzed sila-ene reactions of the corresponding methallylsilanes with SO2 at 50 degrees C. Sterically hindered, epimerizable, and base-sensitive alcohols gave the corresponding silyl ethers in high yields and purities at room temperature and under neutral conditions. As the byproducts of the silylation reaction (SO2+isobutylene) are volatile, the workup was simplified to solvent evaporation. The developed method can be employed for the chemo- and regioselective semiprotection of polyols and glycosides and for the silylation of unstable aldols. The high reactivity of the developed reagents is shown by the synthesis of sterically hindered per-O-tert-butyldimethylsilyl--d-glucopyranose, the X-ray crystallographic analysis of which is the first for a per-O-silylated hexopyranose. The per-O-silylation of polyols, hydroxy carboxylic acids, and carbohydrates with trimethylsilyl 2-methylprop-2-ene-1-sulfinate was coupled with the GC analysis of nonvolatile polyhydroxy compounds both qualitatively and quantitatively.chemoselectivitygas chromatographyregioselectivitysilyl sulfinatessilylationtext::journal::journal article::research article