Selective S-deacetylation inspired by native chemical ligation: practical syntheses of glycosyl thiols and drug mercapto-analogues

Glycosyl thiols are useful building blocks for the construction of compounds of biological and synthetic importance. Herein, we report a practical synthetic approach toward the efficient synthesis of glycosyl thiols via chemo- and regioselective S-deacetylation inspired by native chemical ligation. This strategy allows the large scale synthesis of glycosyl thiols by simple purification steps without column chromatography. In addition, deacetylation reagents (DTT) could also be recovered and regenerated by a simple process. Thiol containing taxol and artemisinin analogues were successfully prepared based on this methodology. Finally, auranofin, a glucose-based oral drug used to treat rheumatoid arthritis, was synthesized in concise steps and overall high yields.