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https://open.uns.ac.rs/handle/123456789/19192
Title: | S–O Acetyl rearrangement in 6-thio-D-glucose derivatives | Authors: | Popsavin Velimir Popsavin Mirjana Miljković Dušan |
Issue Date: | 2018 | Journal: | Journal of the Serbian Chemical Society | Abstract: | © 2018 The Korean Physical Society. All rights reserved. The solvolytic reaction of 1,2-O-isopropylidene-3,6-di-O-(p-toluene-sulphonyl)-α-D-glucofuranose (2), as well as that of 6-chloro-6-deoxy-1,2-O-isopropylidene-3-O-(p-toluenesulphonyl)-α-D-glucofuranose (3), in the presence of potassium thioacetate unexpectedly gave the 6-S-acetyl-5-O-acetyl derivative 5 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-orthoester formation as an intermediate. The regiospecific monosubstitution of the 6-tosyloxy group in compound 2 was successfully achieved with potassium thioacetate, in presence of 2,3-benzo-15-crown-5 as a catalyst. The corresponding 6-S-acetyl derivative 7 was obtained representing a possible intermediate in the mentioned solvolytic reactions. Compound 7 was shown to be very reactive, since it fully transformed into the corresponding mercaptan 8 in the presence of silica gel. This transformation occurred via the same thio-orthoester 7a as in the mentioned solvolytic reactions of furanoses 2 and 3. The synthesized compounds are key intermediates in the planned synthesis of selected natural products and their analogues. | URI: | https://open.uns.ac.rs/handle/123456789/19192 | ISSN: | 0352-5139 | DOI: | 10.2298/JSC180811075P |
Appears in Collections: | PMF Publikacije/Publications |
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