@article{Popsavin_Popsavin_Miljković_2018, place={Belgrade, Serbia}, title={S-O Acetyl rearrangement in 6-thio-D-glucose derivatives}, volume={83}, url={https://www.shd-pub.org.rs/index.php/JSCS/article/view/7240}, DOI={10.2298/JSC180811075P}, abstractNote={Solvolytic reaction of 1,2-<em>O</em>-isopropylidene-3,6-di-<em>O</em>-(<em>p</em>-toluene­sulphonyl)-α-d-glucofuranose (<strong>2</strong>), as well as 6-chloro-6-deoxy-1,2-<em>O</em>-iso­propylidene-α-d-glucofuranose (<strong>3</strong>) in presence of potassium thioacetate unexpectedly gave 6-<em>S</em>-acetyl-5-<em>O</em>-acetyl derivative <strong>5</strong> as the main reaction product. A possible mechanism of these transformations was postulated whereby the main role was ascribed to a neighbouring group participation process, involving hydrogen thio-ortoester formation as an intermediate. Regiospecific monosupstitution of 6-tosyloxy group in compound <strong>2</strong> was successfully achieved with potassium thioacetate, in presence of 1,2-benzo[15,5]crown ether as a catalyst. The corresponding 6-<em>S</em>-acetyl derivative <strong>7</strong> was obtained representing a possible intermediate in the mentioned solvolytic reactions. Compound <strong>7</strong> was shown to be very reactive, since it fully transforms into the corresponding mercaptan <strong>8</strong> in the presence of silica gel. This transformation takes place via the same thio-ortoester <strong>7a</strong> as in the mentioned solvolytic reactions of furanoses <strong>2</strong> and <strong>3</strong>. The synthesized compounds are key intermediates in the planned synthesis of selected natural products and their analogues.}, number={12}, journal={Journal of the Serbian Chemical Society}, author={Popsavin, Velimir and Popsavin, Mirjana and Miljković, Dušan}, year={2018}, month={Dec.}, pages={1297–1303} }