De novo synthesis of 1-deoxythiosugars

Tetrathiomolybdate and Tetraselenotungstate as Sulfur/Selenium Transfer Reagents: Applications in the Synthesis of New Thio/Seleno Sugars

“…Reduction of 1-deoxy-4-thio-D-arabino-2,5lactone 19 with borohydride exchange resin (BER) in methanol produced the thiosugar, 1,4-anhydro-4-thio-D-lyxitol 20 in 67 % yield (Scheme 4). [22] Interestingly, the synthesis of 20 is achieved in three simple steps with an overall yield of 29 %, which is far superior to the only known published report [23] that utilizes eleven linear steps for the synthesis of compound 20 starting from D-xylose.…”

“…A useful and efficient synthesis of biologically relevant thiofuranoses, 1,4-dideoxy-1,4-epithio-D-arabinitol 17 and 1,4-anhydro-4-thio-D-lyxitol 20 and the synthesis of rare thiopyranoses such as 1-deoxythiotalonojirimycin 23 and 1deoxythioidonojirimycin 26 were developed. [22] The methodology involves the synthesis of ditosylates, sulfur transfer reaction with tetrathiomolybdate 1 followed by reduction with borohydride exchange resin (BER). The examples developed through this approach demonstrate the generality of this methodology and wider applicability of the synthesis of 1deoxythiosugars through a protection/ deprotection-free sequence.…”

“…Xylonoditosylate 15 when treated with tetrathiomolybdate 1 in DMSO ). [22] 1,4-Anhydro-4thio-D-arabinitol 17 is the core of many of the natural products such as salaprinol, salacinol, ponkoranol, kotalanol, and de-O-sulfonated kotalanol known especially for the treatment of diabetes mellitus. Unlike the reported synthesis of 17 from D-glucose in 12 steps and from D-xylose which involves nine steps, our method reports a shorter synthesis of 1,4-anhydro-4-thio-Darabinitol 17 from D-xylose.…”

“…To further establish the efficacy of this method, 1,4-anhydro-4-thio-D-lyxitol 20, a pentose sugar, ubiquitous and vital in several biological processes, was synthesized as described in Scheme 4. [22] Tosylation of D-(+)-ribonolactone with tosyl chloride/ pyridine produced ribonoditosylate 18 in 63 % yield. Treatment of ribonoditosylate 18, with tetrathiomolybdate 1 provided 1-deoxy-4-thio-D-arabino-2,5-lactone 19 in good yield (68 %).…”

Design and synthesis of glycomimetics: Recent advances

“…Among the most recent examples, a general one‐pot synthesis of thiosugars 64 by double nucleophilic displacement from various alditol precursors 65 (with xylo‐, ribo‐, manno‐, gluco‐, galacto‐, and fuco‐configurations) was reported by Zhang et al (Figure A). The introduction of sulfur on furanose and pyranose sugar analogues was also described via an intramolecular double displacement of tosylate in α,ω‐di‐ O ‐tosyl aldonolactones (compound of general formula 66 ; Figure B) mediated by the “sulfur transfer” reagent benzyltriethylammonium tetrathiomolybdate [BnEt 3 N] 2 MoS 4 . The subsequent reduction of thiosugar lactones with borohydride exchange resin afforded thiosugars of general formula 67 in good overall yield.…”